Fabric care composition and method comprising a fabric care polysaccharide and wrinkle control agent

ABSTRACT

The present invention relates to fabric care compositions, methods, and articles of manufacture for treating fabrics, comprising an effective amount of fabric care polysaccharides with globular structure. Optionally, the composition can contain other ingredients to improve performance and formulatability. The compositions can be applied to fabric by spraying, soaking, dipping, and can also be used for pre-wash treatment, adding to the wash cycle, adding to the rinse cycle, and/or adding to the drying cycle. Preferably the compositions are applied from spray containers which preferably are in association with instructions for use.

TECHNICAL FIELD

The present invention relates to fabric care compositions, methods, andarticles of manufacture for treating fabrics in order to improve variousproperties of fabrics, in particular, reduction and/or removal ofunwanted wrinkles; fabric wear reduction; fabric pill prevention and/orreduction; and/or fabric color maintenance and/or fading reduction.

BACKGROUND OF THE INVENTION

There is a continuous need for textile technologists to producecompositions and products that provide useful benefits to fabrics,especially clothing, such as maintaining and/or improving a goodappearance, and maintaining fabric condition, e.g., strength and/orsize, and reducing fabric wear, through a simple and convenientapplication of a product.

Consumers commonly judge the desirability and wearability of a garmentby many appearance criteria, such as, absence of wrinkles, absence ofcolor fading, absence of soiling and staining, absence of damage such aspilling, absence of malodor, and the like. Other benefits that consumersvalue include fabric longevity, e.g., fabric wear prevention orreduction, shrinkage prevention or reduction, and the like. Thesebenefits can be more or less provided via textile finishing compositionsthat are applied to fabrics in textile mills and/or garmentmanufacturing facilities, but it is preferable that these benefits areprovided via simple and convenient consumer compositions, methods andproducts, to be applied in the consumer's home. These consumercompositions and products are preferably safe, and do not involvecomplicated and/or unsafe treatments and/or applications. Desirably theycomprise treatments that are familiar to the consumers, such asspraying, soaking, adding to the wash cycle, adding to the rinse cycle,and/or adding to the drying cycle.

The present invention relates to compositions, methods, and articles ofmanufacture that provide some important fabric care benefits, includingat least one of the following: wrinkle removal and/or reduction, fabricstrengthening, fabric wear resistance and/or reduction, fabric pillingprevention and/or reduction, fabric color maintenance and/or fadingreduction, color restoration, fabric soiling reduction, fabric shaperetention, and/or fabric shrinkage reduction.

SUMMARY OF THE INVENTION

The present invention relates to fabric care compositions, fabric caremethods, and articles of manufacture that contain such fabric carecomposition. The fabric care composition comprises:

-   -   (A) an effective amount of fabric care polysaccharide for        providing a fabric with at least one of the following fabric        care benefits: wrinkle removal, wrinkle reduction, wrinkle        resistance, fabric wear reduction, fabric wear resistance,        fabric pilling reduction, fabric color maintenance, fabric color        restoration, fabric color fading reduction, fabric soiling        reduction, fabric soil release, fabric shape retention, and/or        fabric shrinkage reduction, said fabric care polysaccharide        comprises polysaccharides with globular structure and with        molecular weight of from about 5,000 to about 500,000; branched        versions of said polysaccharides; derivatised versions of said        polysaccharides; substituted versions of said polysaccharides;        and mixtures thereof;    -   (B) optionally, from about 0.01% to about 20%, by weight of the        composition, of adjunct fabric care oligosaccharide, selected        from the group consisting of oligosaccharides, oligosaccharide        mixtures, substituted versions of said oligosaccharides and/or        mixtures, derivatised versions of said oligosaccharides and/or        mixtures, and mixtures thereof;    -   (C) optionally, to remove and/or reduce wrinkles, an effective        amount of adjunct wrinkle control agent, preferably selected        from the group consisting of fiber lubricant, fabric shape        retention polymer, lithium salts, and mixtures thereof;    -   (D) optionally, to reduce surface tension, and/or to improve        performance and formulatability, an effective amount of        surfactant;    -   (E) optionally, an effective amount to absorb malodor, of odor        control agent;    -   (F) optionally, an effective amount to provide olfactory effects        of perfume;    -   (G) optionally, an effective amount, to kill, or reduce the        growth of microbes, of antimicrobial active;    -   (H) optionally, an effective amount to provide improved        antimicrobial action of aminocarboxylate chelator;    -   (I) optionally, an effective amount of antimicrobial        preservative, in addition to, or in place of said antimicrobial        active; and    -   (J) optionally, an aqueous carrier; said composition optionally        being essentially free of any material that would soil or stain        fabric under usage conditions.

A preferred fabric care composition for treating fabric comprises aneffective amount of said fabric care polysaccharide with a globularstructure and is applied to fabric and/or an entire fabric garment via,e.g., dipping, soaking, misting and/or spraying processes followed by adrying step. The present invention also relates to the fabric carecompositions incorporated into a spray dispenser and/or mist generator,to create an article of manufacture that can facilitate treatment offabric articles and/or entire fabric garments and/or surfaces with saidcompositions containing fabric care polysaccharide with globularstructure and other optional ingredients at a level that is effective,yet is not discernible when dried on the surfaces.

Also preferred are aqueous or solid, preferably powder, fabric carecompositions for treating fabric in the rinse step, comprising aneffective amount of fabric care polysaccharide with globular structure,and optionally, adjunct fabric care oligosaccharide, fabric softeningactives, perfume, and mixtures thereof.

Other preferred aqueous liquid, or solid, preferably powder or granular,fabric care compositions to be used in the wash cycle comprises aneffective amount of said fabric care polysaccharide with globularstructure, and optionally, adjunct fabric care oligosaccharide,surfactants, builders, perfume, and mixtures thereof.

Also preferred are fabric care compositions for treating fabric in thedrying step, comprising an effective amount of said fabric carepolysaccharide with globular structure, and optionally, adjunct fabriccare oligosaccharide, fabric softening actives, perfume, and mixturesthereof. The dryer-added fabric care composition is preferably providedas part of an article of manufacture in combination with a dispensingmeans such as a flexible substrate or a sprayer which effectivelyreleases the fabric care composition in an automatic tumble clothesdryer.

The fabric care polysaccharides with globular structure can provide atleast some fabric care benefits to all types of fabrics, includingfabrics made of natural fibers, synthetic fibers, and mixtures thereof.

DETAILED DESCRIPTION OF THE INVENTION

The present invention relates to solid or stable, preferablytranslucent, more preferably clear, aqueous fabric care compositions,fabric care methods, and articles of manufacture that use such fabriccare composition. It also relates to the use of fabric carepolysaccharide in a fabric care composition for providing a fabric withat least one of the following fabric care benefits: wrinkle removal,wrinkle reduction, wrinkle resistance, fabric wear reduction, fabricwear resistance, fabric pilling reduction, fabric color maintenance,fabric color fading reduction, fabric color restoration, fabric soilingreduction, fabric soil release, fabric shape retention, and/or fabricshrinkage reduction, said fabric care polysaccharide comprisingpolysaccharides with globular structure and with molecular weight offrom about 5,000 to about 500,000; branched versions of saidpolysaccharides; derivatised versions of said polysaccharides;substituted versions of said polysaccharides; and mixtures thereof.

Said polysaccharides are preferably selected from the group consistingof arabinogalactan, pachyman, curdlan, callose, paramylon,sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan,sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan(OL-2), pustulan, dextran, pullulan and mixtures thereof, branchedversions thereof, substituted versions thereof, derivatised versionsthereof, and mixtures thereof. One class of preferred fabric carepolysaccharides are those having 1,3-β-linked backbone, such as,arabinogalactan, pachyman, curdlan, callose, paramylon, sceleroglucan,lentinan, lichenan, laminarin, szhizophyllan, grifolan, sclerotiniasclerotiorum glucan (SSG), Ompharia lapidescence glucan (OL-2), , andmixtures thereof, branched versions thereof, substituted versionsthereof, derivatised versions thereof, and mixtures thereof, morepreferably arabinogalactan, its derivatised versions, its substitutedversions, and mixtures thereof, typically from about 0.001% to about20%, preferably from about 0.01% to about 10%, more preferably fromabout 0.1% to about 5%, and even more preferably from about 0.1% toabout 2%, by weight of the composition.

Generally, depending on the method of application, the fabric carecompositions of the present invention can be in solid (powder, granules,bars, tablets), dimple tablets, liquid, paste, gel, spray, stick or foamforms.

A preferred fabric care composition for treating fabric comprises aneffective amount of said fabric care polysaccharides with globularstructure, and, optionally, one, or more ingredients selected from thegroup consisting of: adjunct fabric care oligosaccharides, perfume,fiber lubricant, fabric shape retention polymer, lithium salt,hydrophilic plasticizer, odor control agent including cyclodextrin,antimicrobial active and/or preservative, surfactant, fabric softeningactive, static control agent, enzymes, antioxidant, chelating agent,e.g., aminocarboxylate chelating agent, heavy metal chelating agent, dyetransfer inhibiting agent, dye fixative agent, soil release agent,colorant, suds suppressor, insect repelling agent and/or moth repellingagent, and mixtures thereof. The composition is typically applied tofabric and/or an entire fabric garment via a, e.g., dipping, soaking,misting and/or spraying process, followed by a drying step, includingthe process comprising a step of treating and/or spraying and/or mistingthe fabric and/or entire fabric garment with the fabric care compositioneither outside or inside an automatic clothes dryer followed by, orconcurrently with, the drying step in said clothes dryer. Theapplication can be done industrially by large scale processes ontextiles and/or finished garments and clothing, or in a consumer's homeby the use of commercial product.

The fabric care composition of present invention can also be applieddirectly on an entire garment via an applicator, preferably a spraymechanism and/or mist mechanism. When applying the fabric carecomposition of the present invention to an entire garment, it isdesirable that the spraying and/or misting of the entire garment occursin a manner such that excessive amounts of the fabric/garment carecomposition are prevented from being released to the open environment.For example, the spraying and/or misting of the entire garment can occurwithin a bag or other article suitable for containing the garment.

The present invention also relates to concentrated liquid or solidfabric care compositions, which are diluted to form compositions withthe usage concentrations, as given hereinabove and/or hereinbelow, foruse in the “usage conditions”. Concentrated compositions for use in thelaundry process such as pre-wash treatment compositions, wash-addedcompositions, and rinse-added compositions, comprise a higher level offabric care polysaccharide with globular structure, typically from about1% to about 99%, preferably from about 2% to about 65%, more preferablyfrom about 3% to about 25%, by weight of the concentrated fabric carecomposition. Concentrated compositions for use to apply directly tofabric and/or entire garment, such as in the spraying process and/ormisting process and/or dipping/soaking process, comprise a lower level;of fabric care polysaccharide with globular structure, typically fromabout 1% to about 40%, preferably from about 1% to about 25%, morepreferably from about 2% to about 15%, by weight of the concentratedfabric care composition. The concentrated compositions optionallycomprise at least one ingredient selected from the group consisting of:perfume, fiber lubricant, shape retention polymer, lithium salt, odorcontrol agent including cyclodextrin, hydrophilic plasticizer,surfactant, antimicrobial active and/or antibacterial preservative,aminocarboxylate chelating agent, fabric softening active, staticcontrol agent, enzyme, antioxidant, suds suppressor, dye transferinhibiting agent, dye fixing agent, insect repelling agent includingmoth repelling agent, and/or liquid carrier, and mixtures thereof.Concentrated compositions are used in order to provide a less expensiveproduct per use. When a concentrated product is used, i.e., when thefabric care polysaccharide with globular structure is from about 1% toabout 99%, by weight of the concentrated composition, it is preferableto dilute the composition before treating fabric. Preferably, theconcentrated fabric care is diluted with about 50% to about 10,000%,more preferably from about 50% to about 8,000%, and even more preferablyfrom about 50% to about 5,000%, by weight of the composition, of water.Depending on the target fabric care benefit to be provided, theconcentrated compositions should also comprise proportionally higherlevels of the desired optional ingredients to be diluted to be the usagecompositions.

The present invention also relates to aqueous fabric care compositionsincorporated into a spray dispenser and/or mist generator to create anarticle of manufacture that can facilitate treatment of fabric articlesand/or entire fabric garments and/or surfaces with said compositionscontaining said fabric care polysaccharide with globular structure andother optional ingredients at a level that is effective, yet is notdiscernible when dried on the surfaces. The spray dispenser comprisesmanually activated and non-manual powered (operated) spray means and acontainer containing the fabric care composition. The articles ofmanufacture preferably are in association with instructions for use todirect the consumer to apply at least an effective amount of the fabriccare composition and/or fabric care polysaccharide with globularstructure to the fabric to provide the desired benefit.

The present invention also relates to an article of manufacturecomprising the above aqueous fabric care compositions, to be applieddirectly via an applicator, preferably a spray mechanism and/or mistmechanism, more preferably via misting mechanism, on said fabric and/orentire garment in a manner such that excessive amounts of thefabric/garment care composition are prevented from being released to theopen environment, preferably in association with instructions for usewhich direct the consumer to apply at least an effective amount of saidfabric care polysaccharide with globular structure and/or saidcomposition to said fabric and/or entire garment is this manner.

The compositions of the present invention can also be used as ironingaids. An effective amount of the composition can be sprayed onto fabricand the fabric is ironed at the normal temperature at which it should beironed. The fabric can either be sprayed with an effective amount of thecomposition, allowed to dry and then ironed, or sprayed and ironedimmediately. The fabric care polysaccharides of the current inventionhave a molecular weight range that is high enough so that they areeasily damaged by the hot temperature of the ironing process, as is thecase of lower molecular weight oligosaccharides and monosaccharides.

Also preferred is a liquid, preferably aqueous, or solid, preferablypowder, fabric care composition for treating fabric in the rinse step,comprising an effective amount of said fabric care polysaccharide withglobular structure, typically from about 0.05% to about 50%, preferablyfrom about 1% to about 35%, more preferably from about 2% to about 18%,and even more preferably from about 3% to about 10%, by weight of thefabric care composition. The fabric care composition optionallycomprises of: adjunct fabric care oligosaccharide, fabric softeningactive, perfume, electrolyte, chlorine scavenging agent, dye transferinhibiting agent, dye fixing agent, phase stabilizer, chemicalstabilizer including antioxidant, silicone, antimicrobial actives and/orpreservative, chelating agent including aminocarboxylate chelatingagent, colorant, enzyme, brightener, soil release agent, or mixturesthereof. Said composition is preferably packaged into an article ofmanufacture in association with instructions for use to ensure that theconsumer knows what benefits can be achieved, and how best to obtainthese benefits. The present invention also relates to concentratedliquid or solid compositions, which are diluted to form rinse-addedfabric care compositions with the usage concentrations, as givenhereinabove, for use in the “usage conditions”.

Another preferred aqueous or solid, preferably powder or granular,fabric care composition of this invention to be used in the wash cyclecomprises an effective amount of said fabric care polysaccharide withglobular structure, and optionally, adjunct fabric care oligosaccharide,surfactants, builder, perfume, chlorine scavenging agent, dye transferinhibiting agent, dye fixing agent, dispersant, detergent enzyme, heavymetal chelating agent, suds suppressor, fabric softening active,chemical stabilizers including antioxidant, silicone, antimicrobialactive and/or preservative, soil suspending agent, soil release agent,optical brightener, colorant, and the like, or mixtures thereof. Otherwash-added fabric care compositions can be in the form of tablets, bar,paste, gel, spray, stick, foam, and can optionally be contained in apouch or attached to a releasable substrate. These wash-addedcompositions which can be wash additive compositions or detergentcompositions are preferably packaged into an article of manufacture inassociation with instructions for use to ensure that the consumer knowswhat benefits can be achieved, and how best to obtain these benefits.

Also preferred are fabric care compositions for treating fabric in thedrying step, comprising an effective amount of said fabric carepolysaccharide with globular structure, and optionally, adjunct fabriccare oligosaccharides, fabric softening actives, distributing agent,perfume, fiber lubricants, fabric shape retention polymers, lithiumsalts, phase stabilizers, chlorine scavenging agents, dye transferinhibiting agents, dye fixing agents, chemical stabilizers includingantioxidants, silicones, antimicrobial actives and/or preservatives,heavy metal chelating agents, aminocarboxylate chelating agents,enzymes, brighteners, soil release agents, and mixtures thereof. Thefabric care composition can take a variety of physical forms includingliquid, foams, gel and solid forms such as solid particulate forms.However, in the preferred substrate product embodiment, the dryer-addedfabric care composition of the present invention is provided as part ofan article of manufacture in combination with a dispensing means such asa flexible substrate which effectively releases the fabric carecomposition in an automatic tumble clothes dryer. Such dispensing meanscan be designed for single usage or for multiple uses. Preferably thecomposition is applied onto a sheet substrate to form a dryer sheetproduct. The substrates in such products are typically non-woven fabricsubstrates, paper, foams, etc. Typical and preferred dispensing meansare described in U.S. Pat. No. 5,102,564, issued Apr. 7, 1992 to Gardliket al., incorporated herein by reference. Since the characteristics ofthe fabric care polysaccharides with globular structure and otheroptional ingredients that provide the various fabric care benefits canbe different and interfering, it can be desirable to provide some of thefabric care compositions as one, or more, separate compositions, e.g.,as separate areas on a substrate, as disclosed hereinafter. Saidcomposition is preferably packaged with or without a dispensing meansinto an article of manufacture in association with instructions for useto ensure that the consumer knows what benefits can be achieved. Anotherpreferred dispensing means is a sprayer which dispense the liquid fabriccare composition at the beginning and/or during the drying cycle.

The present invention also relates to fabric care compositions fordipping and/or soaking pre-wash treatment containing an effective amountof fabric care polysaccharide with globular structure, and optionally,adjunct fabric care oligosaccharide, surfactants, builders, perfume,chlorine scavenging agents, dye transfer inhibiting agents, dye fixingagents, dispersants, detergent enzymes, heavy metal chelating agents,fabric softening actives, chemical stabilizers including antioxidants,silicones, antimicrobial actives and/or preservatives, soil suspendingagents, soil release agents, optical brighteners, colorants, and thelike, or mixtures thereof. Said composition is preferably packaged inassociation with instructions for use to ensure that the consumer knowswhat benefits can be achieved, and how best to obtain these benefits.The present invention also relates to concentrated liquid or solidcompositions, which are diluted to form pre-wash fabric carecompositions with the usage concentrations, for use in the “usageconditions”.

The present invention also relates to fabric care methods and articlesof manufacture that use such fabric care compositions. Thus the presentinvention relates to the compositions incorporated into a spraydispenser to create an article of manufacture that can facilitatetreatment of fabric surfaces with said fabric care compositionscontaining a fabric care polysaccharide with globular structure andother optional ingredients at a level that is effective, yet is notdiscernible when dried on the surfaces. The spray dispenser comprisesmanually activated and non-manual powered spray means and a containercontaining the fabric care composition. Alternatively, the article ofmanufacture can comprise a fabric care composition and a dispensingmeans to distribute said composition onto the fabrics in a automatictumble clothes dryer. Preferably the dispensing means is a flexiblesubstrate, e.g., in sheet configuration with the fabric care compositionreleasably affixed onto the substrate. For wash-added and rinse-addedmethods, the article of manufacture can simply comprise a liquid orgranular solid fabric care composition and a suitable container.

Preferably the articles of manufacture are in association withinstructions for how to use the composition to treat fabrics correctly,to obtain the desirable fabric care results, viz, wrinkle removal and/orreduction, wrinkle resistance, fiber strengthening/anti-wear, fabricwear reduction, fabric shrinkage prevention and/or reduction, fabricpill prevention and/or reduction, shrinkage prevention and/or reduction,fabric color maintenance, fabric color restoration, fabric color fadingreduction, soiling prevention and/or reduction, soil release, and/orfabric shape retention, and mixtures thereof, including, e.g., themanner and/or amount of composition to used, and the preferred ways ofstretching and/or smoothing of the fabrics. It is important that theinstructions be as simple and clear as possible, so that using picturesand/or icons is desirable.

I. Composition

Fabric Care Polysaccharides

Suitable fabric care polysaccharides for use in the fabric carecomposition of the present invention are those which have a globularconformation in dilute aqueous solution, via a random coiling structure.Said polysaccharides include homo- and/or hetero-polysaccharides withsimple helical structure with or without branching, e.g., with1,4-α-linked backbone structure (e.g., 1,4-α-glucan, 1,4-α-xylan) withor without branching, 1,3-β-linked backbone with or without branching(e.g., galactan), and all 1,6-linked backbones with or without branching(e.g., dextran, pullulan, pustulan), and with a weight-average molecularweight of from about 5,000 to about 500,000, preferably from about 8,000to about 250,000, more preferably from about 10,000 to about 150,000,typically with sizes ranging from about 2 nm to about 300 nm, preferablyfrom about 3 nm to about 100 nm, more preferably from about 4 nm toabout 30 nm. The size is defined as the gyration length occupied by themolecule in dilute aqueous solutions.

Preferably the fabric care polysaccharide is selected from the groupconsisting of arabinogalactan, pachyman, curdlan, callose, paramylon,sceleroglucan, lentinan, lichenan, laminarin, szhizophyllan, grifolan,sclerotinia sclerotiorum glucan (SSG), Ompharia lapidescence glucan(OL-2), pustulan, dextran, pullulan, substituted versions thereof,derivatised versions thereof, and mixtures thereof. More preferably thefabric care polysaccharide is selected from the group consisting ofarabinogalactan, dextran, curdlan, substituted versions thereof,derivatised versions thereof, and mixtures thereof, and even morepreferably the fabric care polysaccharide comprises arabinogalactan,substituted versions thereof, derivatised versions thereof, and mixturesthereof. Substituted and/or derivatised materials of the fabric carepolysaccharides listed hereinabove are also preferred in the presentinvention. Nonlimiting examples of these materials include: carboxyl andhydroxymethyl substitutions (e.g., some uronic acid instead of neutralsugar units); amino polysaccharides (amine substitution); cationicquaternized polysaccharides; C₁–C₁₈ alkylated polysaccharides;acetylated polysaccharide ethers; polysaccharides having amino acidresidues attached (small fragments of glycoprotein); polysaccharidescontaining silicone moieties, and the like. Some hydrophobic derivativesof the polysaccharides help the polysaccharides maintaining the globularconformation.

A preferred class of fabric care polysaccharides suitable for use in thepresent invention include those that have the backbone comprising atleast some, but preferably almost entirely of 1,3-β-glycosidic linkages,preferably branched, preferably with either side chains attached with1,6-linkages or derivatised for better water solubility and/or tomaintain the globular structure. The 1,6-linked branched polysaccharideswith 1,3-β-linked backbone have higher water solubility and/ordispersibility than the non-branched polysaccharides, so that branchedpolysaccharides can be used at higher molecular weight ranges. Insertingother types of linkages, such as some 1,4-β-linkages in the 1,3-β-linkedbackbone also improves the solubility of the polysaccharides.Nonlimiting examples of useful fabric care polysaccharides with1,3-β-linked backbone include arabinogalactan, pachyman, curdlan,callose, paramylon, sceleroglucan, lentinan, lichenan, laminarin,szhizophyllan, grifolan, sclerotinia sclerotiorum glucan (SSG), Ompharialapidescence glucan (OL-2), and mixtures thereof. Low molecular weightmaterials are preferred for polysaccharides with less or no branching,such as curdlan, while higher molecular weight materials for highlybranched polysaccharides, such as arabinogalactan, can be used. Highermolecular weight polysaccharides with mixed 1,3-β and 1,4-β, linkages,such as lichenan, can also be used.

A preferred fabric care branched polysaccharide with 1,3-β-linkedbackbone is arabinogalactan (also named as galactoarabinan orepsilon-galactan). Arabinogalactans are long, densely branchedhigh-molecular weight polysaccharides. Arabinogalactan that is useful inthe composition of the present invention has a molecular weight range offrom about 5,000 to about 500,000, preferably from about 6,000 to about250,000, more preferably from about 10,000 to about 150,000. Thesepolysaccharides are highly branched, consisting of a galactan backbonewith side-chains of galactose and arabinose units (consisting ofβ-galactopyranose, β-arabinofuranose, and β-arabinopyranose). The majorsource of arabinogalactan is the larch tree. The genus Larix (larches)is common throughout the world. Two main sources of larch trees arewestern larch (Larix occidentalis) in Western North America andMongolian larch (Larix dahurica). Examples of other larches are easternlarch (Larix laricina) in eastern North America, European larch (Larixdicidua), Japanese larch (Larix leptolepis), and Siberian larch (Larixsiberica). Most commercial arabinogalactan is produced from westernlarch, through a counter-current extraction process. Larcharabinogalactan is water soluble and is composed of arabinose andgalactose units in about a 1:6 ratio, with a trace of uronic acid.Glycosyl linkage analysis of larch arabinogalactan is consistent with ahighly branched structure comprising a backbone of 1,3-β-linkedgalactopyranose connected by 1,3-β-glycosidic linkages, comprised of3,4,6-, 3,6-, and 3,4- as well as 3-linked residues. The molecularweights of the preferred fractions of larch arabinogalactan include onefraction in the range of from about 14,000 to about 22,000, mainly fromabout 16,000 to about 21,000, and the other in the range of from about60,000 to about 500,000, mainly from about 80,000 to about 120,000. Thefraction that has the average molecular weight of from about 16,000 toabout 20,000 is highly preferred for use in direct applications tofabric, such as in spray-on products. The high molecular weight fraction(of about 100,000 molecular weight), as well as the low molecular weightfraction are suitable for use in processes that involve subsequent watertreatments, such as, pre-soak, wash-added and/or rinse-added laundryprocesses and products. High grade larch arabinogalactan is composed ofgreater than about 98% arabinogalactan. Larch arabinogalactan and someof its derivatives, such as cationic derivatives are commerciallyavailable from Larex, Inc., St Paul, Minn.

Arabinogalactans are also present as minor, water-soluble components ofsoftwoods such as hemlock, black spruce, parana pine, mugo pine, Douglasfir, incense cedar, juniper, and the sapwood of sugar maple. Many edibleand inedible plants are also rich sources of arabinogalactans, mostly inglycoprotein form, bound to a protein spine of either threonine,proline, or serine (“arabinogalactan-protein”). These plants includeleek seeds, carrots, radish, black gram beans, pear, maize, wheat, redwine, Italian ryegrass, tomatoes, ragweed, sorghum, bamboo grass, andcoconut meat and milk. Many herbs with well established immune-enhancingproperties, such as Echinacea purpurea, Baptisia tintoria, Thujaoccidentalis, Angelica acutiloba, and Curcuma longa contain significantamounts of arabinogalactans. Small quantities of arabinogalactans alsooccur in other plants, such as, green coffee bean (sugar ratio about2:5), centrosema seeds (sugar ratio about 1:13), and wheat flour (sugarratio about 7:3). About 70% of the water solubles from soybean flour isan arabinogalactan with a sugar ratio of about 1:2.

Examples of other fabric care polysaccharides that have 1,3-β-linkage asa part of the backbone include: 1,3-β-xylan (from, e.g., Pencillusdumetosus), curdlen, a 1,3-β-glucan (from e.g., Alcaligenes faecalis),paramylon B, a 1,3-β-glucan (from, e.g., Euglena gracilis), lichenin, a(1,3),(1,4)-β-glucan (from various sources including Cetrariaislandica), sceleroglucan, a (1,3),(1,6)-β-glucan (from, e.g.,Sclerotium rolfii), and lentinen, a (1,3),(1,6)-β-glucan (from, e.g.,Lentinus edodes). More details about these and other polysaccharideswith 1,3-β-linked backbone are given in “Chemistry and Biology of(1→3)-β-Glucans”, B. A. Stone and A. E. Clarke, La Trobe UniversityPress, Victoria, Australia, 1992, pp. 68–71, and 82–83, incorporatedherein by reference.

Substituted and/or derivatised materials of arabinogalactans are alsopreferred in the present invention. Nonlimiting examples of thesematerials include: carboxyl and hydroxymethyl substitutions (e.g., someuronic acid instead of neutral sugar units); amino polysaccharides(amine substitution); cationic quaternized polysaccharides; C₁–C₁₈alkylated polysaccharides; acetylated polysaccharide ethers;polysaccharides having amino acid residues attached (small fragments ofglycoprotein); polysaccharides containing silicone moieties. Thesesubstituted and/or derivatised polysaccharides can provide additionalbenefits, such as: amine substitution can bind and/or condense withoxidatively damaged regions of the fiber to rejuvenate aged fabrics;acetylated sugar ethers can serve as bleach activators in subsequentprocesses where hydrogen peroxide is present; polysaccharides havingamino acid residues can improve delivery of fabric care benefits forfabrics containing proteinaceous fibers, e.g., wool and silk; andsilicone-derivatised polysaccharides can provide additional fabricsoftness and lubricity. Examples of derivatised arabinogalactan includethe 3-chloro-2-hydroxypropyltrimethyl ammonium chloride derivative,available from Larex, Inc and the arabinogalactan-proteins givenhereinabove.

The 1,3-β-linked backbone of the fabric care polysaccharides of thepresent invention (as in 1,3-β-galactans, 1,3-β-D-mannans,1,3-β-D-xylans and 1,3-β-D-glucans) has a pseudohelical conformation. Assuch, these polysaccharides have a backbone chain that is flexible andin aqueous solution, has a tendency to coil into a globular structure tosubstantially reduce their apparent dimension (gyration volume), asopposed to the backbone chain of 1,4-β-glucan which has an extendeddimension. The polysaccharides with 1,3-β-linked backbone and extensivebranching via 1,6-linkages, or polysaccharides with helical confirmationor polysaccharides with 1,6-linked backbone have added flexibility dueto the “coiling” nature of the 1,6-linkages. In water thesepolysaccharides with 1,3-β-linked backbone and 1,6-branching, e.g.,arabinogalactans, have a globular conformation with high flexibility tocoil into compact, flexible and deformable microscopic particles. Forexample, an arabinogalactan having a nominal molecular weight of about18,000 has a size (gyration length) of only from 5 nm to about 10 nm indilute aqueous solutions. This structural feature of the globularpolysaccharides with helical conformation and random coiling natureimproves physical properties such as water-solubility, low viscosity andemulsification. It is believed that the globular, compact and flexiblestructural property and low viscosity of the fabric care polysaccharideswith 1,3-β-linked backbone of the present invention, such asarabinogalactans, is important for providing the fabric care benefits,either via efficient deposition of the polysaccharide globules on therough fabric surface or via appropriate fitting/filling of theseglobules in the openings and/or defective spaces on the fabric fibersurface, where they can orient itself to conform to the space available.Furthermore, it is believed that at low levels, these low molecularweight (about 10,000 to about 150,000) polysaccharide globules of thepresent invention can very effectively bond fibers and/or microfibrilstogether by “spot bonding”. This way, the fabric care polysaccharideglobules can provide many desired benefits such as: fabricstrengthening, fabric wear resistance and/or reduction, wrinkle removaland/or reduction, fabric pilling prevention and/or reduction, fabriccolor maintenance and/or fading reduction, color restoration, fabricsoiling reduction, fabric shape retention, fabric shrinkage reduction,and/or improving fabric feel/smoothness, scratchiness reduction, fordifferent types of fabrics such as cellulosic (cotton, rayon, etc.),wool, silk, and the like.

Polysaccharides with helical conformation, but not within the range ofthe molecular weight range specified above have different physicalproperties such as low solubility and gelling characteristics (e.g.,starch, a high molecular weight 1,4-α-D-glucan).

The fabric care polysaccharides with globular structure of the presentinvention can provide at least some fabric care benefits to all types offabrics, including fabrics made of natural fibers, synthetic fibers, andmixtures thereof. Nonlimiting examples of fabric types that can betreated with the fabric care compositions of the present invention, toobtain fabric care benefits include fabrics made of (1) cellulosicfibers such as cotton, rayon, linen, Tencel, (2) proteinaceous fiberssuch as silk, wool and related mammalian fibers, (3) synthetic fiberssuch as polyester, acrylic, nylon, and the like, (4) long vegetablefibers from jute, flax, ramie, coir, kapok, sisal, henequen, abaca, hempand sunn, and (5) mixtures thereof. Other unanimated substrates and/orsurfaces made with natural fibers and/or synthetic fibers, and/ormaterials, such as non-woven fabrics, paddings, carpets, paper,disposable products, films, foams, can also be treated with the fabriccare polysaccharides with 1,3-β-linked backbone to improve theirproperties.

For specific applications, the composition can contain from about 0.001%to about 20% of fabric care polysaccharide with globular structure,preferably from about 0.01% to about 10%, more preferably from about0.1% to about 5%, by weight of the usage composition. The presentinvention also relates to concentrated liquid or solid compositions,which are diluted to form compositions with the usage concentrations,for use in the “usage conditions”. Concentrated compositions comprise ahigher level of fabric care polysaccharide, typically from about 1% toabout 99%, preferably from about 2% to about 65%, more preferably fromabout 3% to about 40%, by weight of the concentrated fabric carecomposition. Depending on the target fabric care benefit to be provided,the concentrated compositions should also comprise proportionally higherlevels of the desired optional ingredients.

Typical composition to be dispensed from a sprayer contains a level offabric care polysaccharide with globular structure of from about 0.01%to about 5%, preferably from about 0.05% to about 2%, more preferablyfrom about 0.1% to about 1%, by weight of the usage composition. Typicalusage compositions for a direct dipping and/or soaking treatmentfollowed by a drying step, contain a level of fabric care polysaccharideof from about 0.001% to about 2%, preferably from about 0.05% to about1%, more preferably from about 0.1% to about 0.5%, by weight of theusage composition. It is also common and practical to provide a moreconcentrated composition containing typically from about 0.5% to about40%, preferably from about 1% to about 25%, more preferably from about2% to about 15%, by weight of the concentrated composition, of fabriccare polysaccharide with globular structure, to be diluted down in useto obtain the desirable usage dipping or soaking composition. Dependingon the target fabric care benefit to be provided, the concentratedcompositions should also comprise proportionally higher levels of thedesired optional ingredients. A concentrated composition can also beused, and is provided, e.g., as a refill, to prepare usage compositionfor the spray product.

Wash-added compositions, including liquid and granular detergentcompositions and wash additive compositions typically contain a level offabric care polysaccharide with globular structure of from about 0.2% toabout 30%, preferably from about 1% to about 20%, more preferably fromabout 2% to about 10%, by weight of the wash-added compositions.

Typical rinse-added compositions, including liquid fabric conditionerand other rinse additive compositions, contain a level of fabric carepolysaccharide with globular structure of from about 0.3% to about 40%,preferably from about 1% to about 25%, more preferably from about 2% toabout 15%, by weight of the rinse-added compositions.

Typical usage compositions for a dipping and/or soaking pre-washtreatment and/or for use as a wash-cycle additive contain a level offabric care polysaccharide with globular structure of from about 0.05%to about 40%, preferably from about 0.1% to about 20%, more preferablyfrom about 0.5% to about 10%, by weight of the usage composition. Moreconcentrated compositions comprise a higher level of fabric carepolysaccharide, typically from about 1% to about 99%, preferably fromabout 2% to about 65%, more preferably from about 3% to about 40%, byweight of the concentrated fabric care composition. Depending on thetarget fabric care benefit to be provided, the concentrated compositionsshould also comprise proportionally higher levels of the desiredoptional ingredients.

Dryer-added compositions typically contain a level of fabric carepolysaccharide with globular structure of from about 0.01% to about 40%by weight of the dryer-added compositions.

Adjunct Fabric Care Oligosaccharides

An optional but preferred adjunct fabric care agent in the presentinvention is selected from the group consisting of oligosaccharides,especially mixtures of oligosaccharides, especially,isomaltooligosaccharides (IMO) (including mixtures), the individualcomponents of said mixtures, substituted versions thereof, derivatisedversions thereof, and mixtures thereof. The adjunct fabric fabric careoligosaccharides help to provide some fabric benefits, such as wrinkleremoval and/or reduction, anti-pilling, anti-wear, fabric colormaintenance, and overall appearance benefits, especially to cellulosicfibers/fabrics, such as cotton, rayon, ramie, jute, flax, linen,polynosic-fibers, Lyocell (Tencel®), polyester/cotton blends, othercotton blends, and the like, especially cotton, rayon, linen,polyester/cotton blends, and mixtures thereof.

Suitable adjunct fabric care oligosaccharides that are useful in thepresent invention include oligosaccharides with a degree ofpolymerization (DP) of from about 1 to about 15, preferably from about 2to about 10, and wherein each monomer is selected from the groupconsisting of reducing saccharide containing 5 and/or 6 carbon atoms,including isomaltose, isomaltotriose, isomaltotetraose,isomaltooligosaccharide, fructooligosaccharide, levooligosaccharides,galactooligosaccharide, xylooligosaccharide, gentiooligosaccharides,disaccharides, glucose, fructose, galactose, xylose, mannose, arabinose,rhamnose, maltose, sucrose, lactose, maltulose, ribose, lyxose, allose,altrose, gulose, idose, talose, trehalose, nigerose, kojibiose,lactulose, oligosaccharides, maltooligosaccharides, trisaccharides,tetrasaccharides, pentasaccharides, hexasaccharides, oligosaccharidesfrom partial hydrolysates of natural polysaccharide sources, and thelike, and mixtures thereof, preferably mixtures ofisomaltooligosaccharides, especially mixtures includingisomaltooligosaccharides, comprising from about 3 to about 7 units ofglucose, respectively, and which are linked by 1,2-α, 1,3-α, 1,4-α- and1,6-α-linkages, and mixtures of these linkages. Oligosaccharidescontaining β-linkages are also preferred. Preferred oligosaccharides areacyclic and have at least one linkage that is not an α-1,4-glycosidicbond. A preferred oligosaccharide is a mixture containing IMO: from 0 toabout 20% by weight of glucose, from about 10 to about 65% ofisomaltose, from about 1% to about 45% of each of isomaltotriose,isomaltetraose and isomaltopentaose, from 0 to about 3% of each ofisomaltohexaose, isomaltoheptaose, isomaltooctaose and isomaltononaose,from about 0.2% to about 15% of each of isomaltohexaose andisomaltoheptaose, and from 0 to about 50% by weight of said mixturebeing isomaltooligosaccharides of 2 to 7 glucose units and from 0 toabout 10% by weight of said mixture being isomaltooligosaccharides ofabout 7 to about 10 glucose units. Other nonlimiting examples ofpreferred acyclic oligosaccharides, with approximate content by weightpercent, are:

Isomaltooligosaccharide Mixture I

Isomaltooligosaccharide Mixture I Trisaccharides (maltotriose, panose,isomaltotriose) 40–65% Disaccharides (maltose, isomaltose)  5–15%Monosaccharide (glucose)  0–20% Higher branched sugars (4 < DP < 10)10–30% Isomaltooligosaccharide Mixture II Trisaccharides (maltotriose,panose, isomaltotriose) 10–25% Disaccharides (maltose, isomaltose)10–55% Monosaccharide (glucose) 10–20% Higher branched sugars (4 < DP <10)  5–10% Isomaltooligosaccharide Mixture III Tetrasaccharides(stachyose) 10–40% Trisaccharides (raffinose)  0–10% Disaccharides(sucrose, trehalose) 10–50% Monosaccharide (glucose, fructose)  0–10%Other higher branched sugars (4 < DP < 10) 0–5%

Oligosaccharide mixtures are either prepared by enzymatic reactions orseparated as natural products from plant materials. The enzymaticsynthesis of oligosaccharides involves either adding monosaccharides,one at a time, to a di- or higher saccharide to produce branchedoligosaccharides, or it can involve the degradation of polysaccharidesfollowed by transfer of saccharides to branching positions. Forinstance, Oligosaccharide Mixtures I and II are prepared by enzymatichydrolysis of starch to maltooligosaccharides, which are then convertedto isomaltooligosaccharides by a transglucosidase reaction.Oligosaccharide Mixture III, for example, is a mixture ofoligosaccharides isolated from soybean. Soybean oligosaccharides such asMixture III, are of pure natural origin.

Cyclic oligosaccharides can also be useful in the fabric carecomposition of the present invention. Preferred cyclic oligosaccharidesinclude α-cyclodextrin, β-cyclodextrin, γ-cyclodextrin, their branchedderivatives such as glucosyl-α-cyclodextrin, diglucosyl-α-cyclodextrin,maltosyl-α-cyclodextrin, glucosyl-β-cyclodextrin,diglucosyl-β-cyclodextrin, and mixtures thereof. The cyclodextrins alsoprovide an optional but very important benefit of odor control, and aredisclosed more fully hereinbelow.

Substituted and/or derivatised materials of the oligosaccharides listedhereinabove are also preferred in the present invention. Nonlimitingexamples of these materials include: carboxyl and hydroxymethylsubstitutions (e.g., glucuronic acid instead of glucose); aminooligosaccharides (amine substitution, e.g., glucosamine instead ofglucose); cationic quaternized oligosaccharides; C₁–C₆ alkylatedoligosaccharides; acetylated oligosaccharide ethers; oligosaccharideshaving amino acid residues attached (small fragments of glycoprotein);oligosaccharides containing silicone moieties. These substituted and/orderivatised oligosaccharides can provide additional benefits, such as:carboxyl and hydroxymethyl substitutions can introduce readilyoxidizable materials on and in the fiber, thus reducing the probabilityof the fiber itself being oxidized by oxidants, such as bleaches; aminesubstitution can bind and/or condense with oxidatively damaged regionsof the fiber to rejuvenate aged fabrics; acetylated sugar ethers canserve as bleach activators in subsequent processes where hydrogenperoxide is present; oligosaccharides having amino acid residues canimprove delivery of fabric care benefits for fabrics containingproteinaceous fibers, e.g., wool and silk; and silicone-derivatisedoligosaccharides can provide additional fabric softness and lubricity.C₆ alkyl oligosaccharide is disclosed (along with other higher, viz.,C₆–C₃₀, alkyl polysaccharides) in U.S. Pat. No. 4,565,647, issued Jan.21, 1986 to Llenado, for use as foaming agent in foaming compositionssuch as laundry detergents, personal and hair cleaning compositions, andfire fighting compositions. The C₆ alkyl oligosaccharide is a poorsurfactant and not preferred for use as surfactant in the detergentcompositions of the present invention, but preferably can be used toprovide the fabric care benefits that are not known, appreciated and/ordisclosed in U.S. Pat. No. 4,565,647. U.S. Pat. No. 4,488,981, issuedDec. 18, 1984 discloses the use of some C₁–C₆ alkylated oligosaccharides(lower alkyl glycosides) in aqueous liquid detergents to reduce theirviscosity and to prevent phase separation. C₁–C₆ alkylatedoligosaccharides are not preferred for use as viscosity and phasemodifiers in the liquid detergent compositions of the present invention,but can be used to provide the fabric care benefits that are not known,appreciated and/or disclosed in U.S. Pat. No. 4,488,981. These patentsare incorporated herein by reference.

It is believed that the fabric care oligosaccharide is adsorbed andbinds with cellulosic fabrics to improve the properties of the fabrics.It is believed that the fabric care oligosaccharide is bound to thecellulosic fibers, diffuses in and fills the defect sites (the amorphousregion) of the fiber, to provide the above dewrinkling, increasedstrength and improved appearance benefits. The extent of the amorphous,non-crystalline region varies with cellulosic fiber types, e.g., therelative crystallinity of cotton is about 70. % and for regeneratedcellulose, such as, rayon it is about 30. %, as reported by P. H.Hermans and A. Weidinger, “X-ray studies on the crystallinity ofcellulose” in the Journal of Polymer Science, Vol IV, p135–144, 1949. Itis believed that the amorphous regions are accessible for chemical andphysical modifications, and that in the durable press treatment, theamorphous regions are filled with molecules that can crosslink cellulosepolymers by covalent bonds, to deliver wrinkle-free benefits (cf. S. P.Rawland, in “Modified Cellulosics,” R. M. Rowell and R. A. Young, Eds.,Academic Press, New York, 1978, pp. 147–167, cited by G. C. Tesoro, in‘Crosslinking of cellulosics’, Handbook of Fiber Science and Technology,Vol. II, p. 6, edited by M. Lewin and S. B. Sello, published by MarcelDekker, 1983. These publications are incorporated herein by reference.

For specific applications, the composition can contain from about 0.001%to about 20% of the optional, but preferred oligosaccharide, preferablyfrom about 0.01% to about 10%, more preferably from about 0.1% to about5%, by weight of the usage composition. The present invention alsorelates to concentrated liquid or solid compositions, which are dilutedto form compositions with the usage concentrations, for use in the“usage conditions”. Concentrated compositions comprise a higher level ofthe optional fabric care oligosaccharide, typically from about 1% toabout 50%, preferably from about 2% to about 40%, more preferably fromabout 3% to about 20%, by weight of the concentrated fabric carecomposition.

Typical composition to be dispensed from a sprayer contains a level ofoptional fabric care oligosaccharide of from about 0.01% to about 3%,preferably from about 0.05% to about 2%, more preferably from about 0.1%to about 1%, by weight of the usage composition. Typical usagecompositions for a direct dipping and/or soaking treatment followed by afabric drying step, contain a level of optional fabric careoligosaccharide of from about 0.001% to about 2%, preferably from about0.05% to about 1%, more preferably from about 0.1% to about 0.5%, byweight of the usage composition. It is also common and more practical toprovide a more concentrated composition containing typically from about1% to about 40%, preferably from about 1% to about 25%, more preferablyfrom about 2% to about 15%, by weight of the concentrated composition,of the optional fabric care oligosaccharide, to be diluted down in useto obtain the desirable usage dipping or soaking compositions. Aconcentrated composition can also be used, and is provided, e.g., as arefill, to prepare usage composition for the spray product.

Wash-added compositions, including liquid and granular detergentcompositions and wash additive compositions typically contain a level ofoptional fabric care oligosaccharide of from about 0.2% to about 30%,preferably from about 1% to about 20%, more preferably from about 2% toabout 12%, by weight of the wash-added compositions. Typical rinse-addedcompositions, including liquid fabric conditioner and other rinseadditive compositions, contain a level of optional fabric careoligosaccharide of from about 0.1% to about 50%, preferably from about1% to about 35%, more preferably from about 2% to about 18%, and evenmore preferably from about 2% to about 10%, by weight of the rinse-addedcompositions.

Dryer-added compositions typically contain a level of optional fabriccare oligosaccharide of from about 0.01% to about 40%, preferably fromabout 0.1% to about 20%, more preferably from about 1% to about 10%, byweight of the dryer-added compositions. Aqueous dryer-added compositionsto be applied directly to the fabric, e.g., via a spraying mechanism,contain lower levels of fabric care polysaccharide, typically from about0.01% to about 25%, preferably from about 0.1% to about 10%, morepreferably from about 0.2% to about 5%, even more preferably from about0.3% to about 3%, by weight of the compositions.

Both the fabric care polysaccharides and the optional fabric careoligosaccharides have a compact structure, but they have differentsizes. The smaller oligosaccharides are believed to be able to diffuseand penetrate into small defective sites, such as the amorphous regionof cotton fibers, while the larger polysaccharides can fill in largeropenings and/or defective sites on the fabric fiber surface. Thereforedepending on the fabric care benefit target, the fabric carepolysaccharides can be used alone, or in mixtures with the optionalfabric care oligosaccharides. When the optional fabric careoligosaccharides are present, the weight ratio between saidoligosaccharides and the fabric care polysaccharides is typically fromabout 1:99 to about 99:1, preferably from about 15:85 to about 85:15,and more preferably from about 30:70 to about 70:30.

Nonlimiting examples of other optional ingredients are givenhereinbelow.

Other Optional Ingredients

The fabric care compositions of the present invention can contain otheroptional ingredients either to improve the performance of the fabriccare polysaccharide with globular structure, e.g., in the areas ofwrinkle control, anti-wear, soil release, and the like, or to provideadditional benefits, such as odor control, antimicrobial, and the like.Nonlimiting examples of optional ingredients are given hereinbelow.

Fiber Lubricants

The fabric care composition of the present invention can compriseoptional fiber lubricants to impart a lubricating property, or increasedgliding ability, to fibers in fabric, particularly clothing. Not to bebound by theory, it is believed that fiber lubricants facilitate themovement of fibers with respect to one another (glide) to release thefibers from the wrinkle condition in wet or damp fabrics. After thefabric is dried, the fiber lubricant, especially silicone, can providelubricity to reduce the tendency of fabric to rewrinkle.

(a). Silicone

The present invention can use silicone, a preferred fiber lubricant, toimpart a lubricating property, or increased gliding ability, to fibersin fabric, particularly clothing. Nonlimiting examples of usefulsilicones in the composition of the present invention include noncurablesilicones such as polydimethylsilicone and volatile silicones, andcurable silicones such as aminosilicones, phenylsilicones andhydroxysilicones. The word “silicone” as used herein preferably refersto emulsified silicones, including those that are commercially availableand those that are emulsified in the composition, unless otherwisedescribed. Preferably, the silicones are hydrophobic; are neitherirritating, toxic, nor otherwise harmful when applied to fabric or whenthey come in contact with human skin; are chemically stable under normaluse and storage conditions; and are capable of being deposited onfabric.

When the composition of this invention is to be dispensed from a spraydispenser in a consumer household setting, the noncurable silicones suchas polydimethylsilicone, especially the volatile silicones, arepreferred. Curable and/or reactive silicones such as amino-functionalsilicones and silicones with reactive groups such as Si—OH, Si—H,silanes, and the like, are less preferred in this situation, because theportion of the composition that is sprayed but misses the garment, andfalls instead on flooring surfaces, such as rug, carpet, concrete floor,tiled floor, linoleum floor, bathtub floor, can leave a silicone layerthat is cured and/or bonded to the flooring surfaces. Such siliconesthat are bonded to surfaces are difficult to be removed from theflooring surfaces. Flooring surfaces thus become slippery and canpresent a safety hazard to the household members. The curable andreactive silicones can be used in compositions specifically designed foruse in articles such as a flexible bag, and in other, non-spray fabrictreatment processes, such as dipping, soaking, in-the-wash,in-the-rinse, and in-the-dryer processes. Many types of aminofunctionalsilicones also cause fabric yellowing. Thus, the silicones that causefabric discoloration are also not preferred.

The preferred silicone is volatile silicone fluid which can be a cyclicsilicone fluid of the formula [(CH₃)₂SiO]_(n) where n ranges betweenabout 3 to about 7, preferably about 5 (D5), or a linear siliconepolymer fluid having the formula (CH₃)₃SiO[(CH₃)₂SiO]_(m)Si(CH₃)₃ wherem can be 0 or greater and has an average value such that the viscosityat 25° C. of the silicone fluid is preferably about 5 centistokes orless.

The non-volatile silicones that are useful and preferred in thecomposition of the present invention is polyalkyl and/or phenylsiliconessilicone fluids and gums with the following structure:A—Si(R₂)—O—[Si(R₂)—O—]_(q)—Si(R₂)—A

The alkyl groups substituted on the siloxane chain (R) or at the ends ofthe siloxane chains (A) can have any structure as long as the resultingsilicones remain fluid at room temperature.

Each R group preferably can be alkyl, aryl, hydroxy, or hydroxyalkylgroup, and mixtures thereof, more preferably, each R is methyl, ethyl,propyl or phenyl group, most preferably R is methyl. Each A group whichblocks the ends of the silicone chain can be hydrogen, methyl, methoxy,ethoxy, hydroxy, propoxy, and aryloxy group, preferably methyl. SuitableA groups include hydrogen, methyl, methoxy, ethoxy, hydroxy, andpropoxy. q is preferably an integer from about 7 to about 8,000. Thepreferred silicones are polydimethyl siloxanes; more preferred siliconesare polydimethyl siloxanes having a viscosity of from about 50 to about1000,000 centistokes at 25° C. Mixtures of volatile silicones andnon-volatile polydimethyl siloxanes are also preferred. Suitableexamples include silicones offered by Dow Corning Corporation andGeneral Electric Company.

Other useful silicone materials, but less preferred than polydimethylsiloxanes, include materials of the formula:HO—[Si(CH₃)₂—O]_(x)—{Si(OH)[(CH₂)₃—NH—(CH₂)₂—NH₂]O}_(y)—Hwherein x and y are integers which depend on the molecular weight of thesilicone, preferably having a viscosity of from about 10,000 cst toabout 500,000 cst at 25° C. This material is also known as“amodimethicone”. Although silicones with a high number, e.g., greaterthan about 0.5 millimolar equivalent of amine groups can be used, theyare not preferred because they can cause fabric yellowing.

Similarly, silicone materials which can be used correspond to theformulas:(R¹)_(a)G_(3-a)—Si—(—OSiG₂)_(n)—(OSiG_(b)(R¹)_(2-b))_(m)—O—SiG_(3-a)(R¹)_(a)wherein G is selected from the group consisting of hydrogen, phenyl, OH,and/or C₁–C₈ alkyl; a denotes 0 or an integer from 1 to 3; b denotes 0or 1; the sum of n+m is a number from 1 to about 2,000; R¹ is amonovalent radical of formula C_(p)H_(2p)L in which p is an integer from2 to 8 and L is selected from the group consisting of:

-   —N(R²)CH₂—CH₂—N(R²)₂;-   —N(R²)₂;-   —N⁺(R²)₃ A⁻; and-   —N⁺(R²)CH₂—CH₂N⁺H₂ A⁻    wherein each R² is chosen from the group consisting of hydrogen,    phenyl, benzyl, saturated hydrocarbon radical, and each A⁻ denotes    compatible anion, e.g., a halide ion; and    R³—N⁺(CH₃)₂—Z—[Si(CH₃)₂O]_(f)—Si(CH₃)₂—Z—N⁺(CH₃)₂—R³.2CH₃COO⁻    wherein    -   Z=—CH₂—CH(OH)—CH₂O—CH₂)₃—    -   R³ denotes a long chain alkyl group; and    -   f denotes an integer of at least about 2.

In the formulas herein, each definition is applied individually andaverages are included.

Another silicone material which can be used, but is less preferred thanpolydimethyl siloxanes, has the formula:(CH₃)₃Si—[O—Si(CH₃)₂]_(n)—{OSi(CH₃)[(CH₂)₃—NH—(CH₂)₂—NH₂]}_(m)—OSi(CH₃)₃wherein n and m are the same as before. The preferred silicones of thistype are those which do not cause fabric discoloration.

Alternatively, the silicone material can be provided as a moiety or apart of a oligosaccharide molecule. These materials provide a lubricitybenefit in addition to the expected fabric care benefits. Other examplesof dual function silicone materials useful in the present invention areadjunct shape retention copolymers having siloxane macromers graftedthereto. The non-silicone backbone of such polymers should have amolecular weight of from about 5,000 to about 1,000,000, and the polymershould have a glass transition temperature (Tg), i.e., the temperatureat which the polymer changes from a brittle vitreous state to a plasticstate, of greater than about −20° C. Adjunct fabric shape retentionsilicone-containing polymers useful in the present invention aredescribed in more detailed herein below along with other adjunct shaperetention polymers.

When silicone is present, it is present at least an effective amount toprovide lubrication of the fibers, typically from about 0.1% to about5%, preferably from about 0.2% to about 3%, more preferably from about0.3% to about 2%, by weight of the usage composition.

Silicone is also a useful optional ingredient in the rinse-added fabriccare compositions of the present invention. The silicone can be either apolydimethyl siloxane (polydimethyl silicone or PDMS), or a derivativethereof, e.g., amino silicones, ethoxylated silicones, etc. The PDMS, ispreferably one with a low molecular weight, e.g., one having a viscosityof from about 2 to about 5000 cSt, preferably from about 5 to about 500cSt, more preferably from about 25 to about 200 cSt. Silicone emulsionscan conveniently be used to prepare the compositions of the presentinvention. However, in compositions containing fabric softening actives,the silicone is preferably one that is, at least initially, notemulsified. I.e., the silicone should be emulsified in the compositionitself. In the process of preparing the compositions, the silicone ispreferably added to the “water seat”, which comprises the water and,optionally, any other ingredients that normally stay in the aqueousphase.

Low molecular weight PDMS is preferred for use in the fabric softenercompositions of this invention. The low molecular weight PDMS is easierto formulate without pre-emulsification.

Silicone derivatives such as amino-functional silicones, quaternizedsilicones, and silicone derivatives containing Si—OH, Si—H, and/or Si—Clbonds, can be used. However, these silicone derivatives are normallymore substantive to fabrics and can build up on fabrics after repeatedtreatments to actually cause a reduction in fabric absorbency.

When added to water, the fabric softener composition deposits thecationic fabric softening active on the fabric surface to provide fabricsoftening effects. However, in a typical laundry process, using anautomatic washer, cotton fabric water absorbency can be appreciablyreduced at high softening active levels and/or after multiple cycles.The silicone improves the fabric water absorbency, especially forfreshly treated fabrics, when used with this level of fabric softeningactive without adversely affecting the fabric softening performance. Themechanism by which this improvement in water absorbency occurs is notwell understood, since the silicones are inherently hydrophobic. It isvery surprising that there is any improvement in water absorbency,rather than additional loss of water absorbency. The PDMS also improvesthe ease of ironing in addition to improving the rewettabilitycharacteristics of the fabrics.

The amount of PDMS needed to provide a noticeable improvement in waterabsorbency is dependent on the initial rewettability performance, which,in turn, is dependent on the detergent type used in the wash. Effectiveamounts range from about 2 ppm to about 50 ppm in the rinse water,preferably from about 5 to about 20 ppm. The PDMS to softening activeratio is from about 2:100 to about 50:100, preferably from about 3:100to about 35:100, more preferably from about 4:100 to about 25:100. Thistypically requires from about 0.2% to about 20%, preferably from about0.5% to about 10%, more preferably from about 1% to about 5% silicone.

(b). Synthetic Solid Particles

Solid polymeric particles of average particle size smaller than about 10microns, preferably smaller than 5 microns, more preferably smaller thanabout 1 micron, e.g., Velustrol P-40 oxidized polyethylene emulsionavailable from Clariant, can be used as a lubricant, since they canprovide a “roller-bearing” action. When solid polymeric particles arepresent, they are present at an effective amount to provide lubricationof the fibers, typically from about 0.01% to about 3%, preferably fromabout 0.05% to about 1%, more preferably from about 0.1% to about 0.5%,by weight of the usage composition.

Adjunct Fabric Shape Retention Polymer

These polymers can be natural, or synthetic, and can act by forming afilm, and/or by providing adhesive properties. E.g., the presentinvention can optionally use film-forming and/or adhesive polymer toimpart shape retention to fabric, particularly clothing. By “adhesive”it is meant that when applied as a solution or a dispersion to a fibersurface and dried, the polymer can attach to the surface. The polymercan form a film on the surface, or when residing between two fibers andin contact with the two fibers, it can bond the two fibers together.Other polymers such as starches can form a film and/or bond the fiberstogether when the treated fabric is pressed by a hot iron. Such a filmwill have adhesive strength, cohesive breaking strength, and cohesivebreaking strain.

Nonlimiting examples for natural polymers are starches and theirderivatives, and chitins and their derivatives.

The synthetic polymers useful in the present invention are comprised ofmonomers. Some nonlimiting examples of monomers which can be used toform the synthetic polymers of the present invention include: lowmolecular weight C₁–C₆ unsaturated organic mono-carboxylic andpolycarboxylic acids, such as acrylic acid, methacrylic acid, crotonicacid, maleic acid and its half esters, itaconic acid, and mixturesthereof; esters of said acids with C₁–C₁₂ alcohols, such as methanol,ethanol, 1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol,1-pentanol, 2-pentanol, 3-pentanol, 2-methyl-1-butanol,1-methyl-1-butanol, 3-methyl-1-butanol, 1-methyl-1-pentanol,2-methyl-1-pentanol, 3-methyl-1-pentanol, t-butanol, cyclohexanol,2-ethyl-1-butanol, neodecanol, 3-heptanol, benzyl alcohol, 2-octanol,6-methyl-1-heptanol, 2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol,3,5,5-trimethyl-1-hexanol, 1-decanol, 1-dodecanol, and the like, andmixtures thereof. Nonlimiting examples of said esters are methylacrylate, ethyl acrylate, t-butyl acrylate, methyl methacrylate,hydroxyethyl methacrylate, methoxy ethyl methacrylate, and mixturesthereof; amides and imides of said acids, such asN,N-dimethylacrylamide, N-t-butyl acrylamide, maleimides; low molecularweight unsaturated alcohols such as vinyl alcohol (produced by thehydrolysis of vinyl acetate after polymerization), allyl alcohol; estersof said alcohols with low molecular weight carboxylic acids, such as,vinyl acetate, vinyl propionate; ethers of said alcohols such as methylvinyl ether; aromatic vinyl such as styrene, alpha-methylstyrene,t-butylstyrene, vinyl toluene, polystyrene macromer, and the like; polarvinyl heterocyclics, such as vinyl pyrrolidone, vinyl caprolactam, vinylpyridine, vinyl imidazole, and mixtures thereof; other unsaturatedamines and amides, such as vinyl amine, diethylene triamine,dimethylaminoethyl methacrylate, ethenyl formamide; vinyl sulfonate;salts of acids and amines listed above; low molecular weight unsaturatedhydrocarbons and derivatives such as ethylene, propylene, butadiene,cyclohexadiene, vinyl chloride; vinylidene chloride; and mixturesthereof and alkyl quaternized derivatives thereof, and mixtures thereof.Preferably, said monomers are selected from the group consisting ofvinyl alcohol; acrylic acid; methacrylic acid; methyl acrylate; ethylacrylate; methyl methacrylate; t-butyl acrylate; t-butyl methacrylate;n-butyl acrylate; n-butyl methacrylate; isobutyl methacrylate;2-ethylhexyl methacrylate; dimethylaminoethyl methacrylate; N,N-dimethylacrylamide; N,N-dimethyl methacrylamide; N-t-butyl acrylamide;vinylpyrrolidone; vinyl pyridine; adipic acid; diethylenetriamine; saltsthereof and alkyl quaternized derivatives thereof, and mixtures thereof.

Preferably, said monomers form homopolymers and/or copolymers (i.e., thefilm-forming and/or adhesive polymer) having a glass transitiontemperature (Tg) of from about −20° C. to about 150° C., preferably fromabout −10° C. to about 150° C., more preferably from about 0° C. toabout 100° C., most preferably, the adhesive polymer hereof, when driedto form a film will have a Tg of at least about 25° C., so that they arenot unduly sticky, or “tacky” to the touch. Preferably said polymer issoluble and/or dispersible in water and/or alcohol. Said polymertypically has a molecular weight of at least about 500, preferably fromabout 1,000 to about 2,000,000, more preferably from about 5,000 toabout 1,000,000, and even more preferably from about 30,000 to about300,000 for some polymers.

Some non-limiting examples of homopolymers and copolymers which can beused as film-forming and/or adhesive polymers of the present inventionare: adipic acid/dimethylaminohydroxypropyl diethylenetriaminecopolymer; adipic acid/epoxypropyl diethylenetriamine copolymer;poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinylalcohol; polyvinylpyridine n-oxide; methacryloyl ethylbetaine/methacrylates copolymer; ethyl acrylate/methylmethacrylate/methacrylic acid/acrylic acid copolymer; polyamine resins;and polyquaternary amine resins; poly(ethenylformamide);poly(vinylamine) hydrochloride; poly(vinyl alcohol-co-6% vinylamine);poly(vinyl alcohol-co-12% vinylamine); poly(vinyl alcohol-co-6%vinylamine hydrochloride); and poly(vinyl alcohol-co-12% vinylaminehydrochloride). Preferably, said copolymer and/or homopolymers areselected from the group consisting of adipicacid/dimethylaminohydroxypropyl diethylenetriamine copolymer;poly(vinylpyrrolidone/dimethylaminoethyl methacrylate); polyvinylalcohol; ethyl acrylate/methyl methacrylate/methacrylic acid/acrylicacid copolymer; methacryloyl ethyl betaine/methacrylates copolymer;polyquaternary amine resins; poly(ethenylformamide); poly(vinylamine)hydrochloride; poly(vinyl alcohol-co-6% vinylamine); poly(vinylalcohol-co-12% vinylamine); poly(vinyl alcohol-co-6% vinylaminehydrochloride); and poly(vinyl alcohol-co-12% vinylamine hydrochloride).

Nonlimiting examples of the preferred polymer that are commerciallyavailable are: polyvinylpyrrolidone/dimethylaminoethyl methacrylatecopolymer, such as Copolymer 958®, molecular weight of about 100,000 andCopolymer 937, molecular weight of about 1,000,000, available from GAFChemicals Corporation; adipic acid/dimethylaminohydroxypropyldiethylenetriamine copolymer, such as Cartaretin F-4® and F-23,available from Sandoz Chemicals Corporation; methacryloyl ethylbetaine/methacrylates copolymer, such as Diaformer Z-SM®, available fromMitsubishi Chemicals Corporation; polyvinyl alcohol copolymer resin,such as Vinex 2019® available from Air Products and Chemicals orMoweol®, available from Clariant; adipic acid/epoxypropyldiethylenetriamine copolymer, such as Delsette 101®, available fromHercules Incorporated; polyamine resins, such as Cypro 515®, availablefrom Cytec Industries; polyquaternary amine resins, such as Kymene557H®, available from Hercules Incorporated; andpolyvinylpyrrolidone/acrylic acid, such as Sokalan EG 310®, availablefrom BASF.

Preferred polymers useful in the present invention are selected from thegroup consisting of copolymers of hydrophilic monomers and hydrophobicmonomers. The polymer can be linear random or block copolymers, andmixtures thereof. Such hydrophobic/hydrophilic copolymers typically havea hydrophobic monomer/hydrophilic monomer ratio of from about 95:5 toabout 20:80, preferably from about 90:10 to about 40:60, more preferablyfrom about 80:20 to about 50:50 by weight of the copolymer. Thehydrophobic monomer can comprise a single hydrophobic monomer or amixture of hydrophobic monomers, and the hydrophilic monomer cancomprise a single hydrophilic monomer or a mixture of hydrophilicmonomers. The term “hydrophobic” is used herein consistent with itsstandard meaning of lacking affinity for water, whereas “hydrophilic” isused herein consistent with its standard meaning of having affinity forwater. As used herein in relation to monomer units and polymericmaterials, including the copolymers, “hydrophobic” means substantiallywater insoluble; “hydrophilic” means substantially water soluble. Inthis regard, “substantially water insoluble” shall refer to a materialthat is not soluble in distilled (or equivalent) water, at 25° C., at aconcentration of about 0.2% by weight, and preferably not soluble atabout 0.1% by weight (calculated on a water plus monomer or polymerweight basis). “Substantially water soluble” shall refer to a materialthat is soluble in distilled (or equivalent) water, at 25° C., at aconcentration of about 0.2% by weight, and are preferably soluble atabout 1% by weight. The terms “soluble”, “solubility” and the like, forpurposes hereof, corresponds to the maximum concentration of monomer orpolymer, as applicable, that can dissolve in water or other solvents toform a homogeneous solution, as is well understood to those skilled inthe art.

Nonlimiting examples of useful hydrophobic monomers are acrylic acidC₁–C₁₈ alkyl esters, such as methyl acrylate, ethyl acrylate, t-butylacrylate; methacrylic C₁–C₁₈ alkyl esters, such as methyl methacrylate,2-ethyl hexyl methacrylate, methoxy ethyl methacrylate; vinyl alcoholesters of carboxylic acids, such as, vinyl acetate, vinyl propionate,vinyl neodecanoate; aromatic vinyls, such as styrene, t-butyl styrene,vinyl toluene; vinyl ethers, such as methyl vinyl ether; vinyl chloride;vinylidene chloride; ethylene, propylene and other unsaturatedhydrocarbons; and the like; and mixtures thereof. Some preferredhydrophobic monomers are methyl acrylate, methyl methacrylate, t-butylacrylate, t-butyl methacrylate, n-butyl acrylate, n-butyl methacrylate,and mixtures thereof.

Nonlimiting examples of useful hydrophilic monomers are unsaturatedorganic mono-carboxylic and polycarboxylic acids, such as acrylic acid,methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid; unsaturated alcohols, such as vinyl alcohol, allylalcohol; polar vinyl heterocyclics, such as vinyl pyrrolidone, vinylcaprolactam, vinyl pyridine, vinyl imidazole; vinyl amine; vinylsulfonate; unsaturated amides, such as acrylamides, e.g.,N,N-dimethylacrylamide, N-t-butyl acrylamide; hydroxyethyl methacrylate;dimethylaminoethyl methacrylate; salts of acids and amines listed above;and the like; and mixtures thereof. Some preferred hydrophilic monomersare acrylic acid, methacrylic acid, N,N-dimethyl acrylamide,N,N-dimethyl methacrylamide, N-t-butyl acrylamide, dimethylamino ethylmethacrylate, vinyl pyrrolidone, salts thereof and alkyl quaternizedderivatives thereof, and mixtures thereof.

Non limiting examples of polymers for use in the present inventioninclude the following, where the composition of the copolymer is givenas approximate weight percentage of each monomer used in thepolymerization reaction used to prepare the polymer: vinylpyrrolidone/vinyl acetate copolymers (at ratios of up to about 30% byweight of vinyl pyrrolidone); dimethyl acrylamide/t-butyl acrylate/ethylhexyl methacrylate copolymer (10/45/45); vinyl pyrrolidone/vinylacetate/butyl acrylate copolymer (10/78/12 and 10/70/20); vinylpyrrolidone/vinyl propionate copolymer (5/95); vinyl caprolactam/vinylacetate copolymer (5/95); acrylic acid/t-butyl acrylate (25/75) andstyling resins sold under the trade names Ultrahold CA 8® by Ciba Geigy(ethyl acrylate/acrylic acid/N-t-butyl acrylamide copolymer); Resyn28-1310® by National Starch and Luviset CA 66® by BASF (vinylacetate/crotonic acid copolymer 90/10); Luviset CAP® by BASF (vinylacetate/vinyl propionate/crotonic acid 50/40/10); Resyn 28-2930® byNational Starch (vinyl acetate/vinyl neodecanoate/crotonic acidcopolymer), Amerhold DR-25® by Union Carbide (ethyl acrylate/methacrylicacid/methyl methacrylate/acrylic acid copolymer), and Poligen A® by BASF(polyacrylate dispersion).

Preferably, the adjunct shape retention polymers contain an effectiveamount of monomers having carboxylic groups. Highly preferred adjunctshape retention copolymers contain hydrophobic monomers and hydrophilicmonomers which comprise unsaturated organic mono-carboxylic andpolycarboxylic acid monomers, such as acrylic acid, methacrylic acid,crotonic acid, maleic acid and its half esters, itaconic acid, and saltsthereof, and mixtures thereof; and optionally other hydrophilicmonomers. Examples of the hydrophilic unsaturated organicmono-carboxylic and polycarboxylic acid monomers are acrylic acid,methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and mixtures thereof. Nonlimiting examples of thehydrophobic monomers are esters of the unsaturated organicmono-carboxylic and polycarboxylic acids cited hereinabove with C₁–C₁₂alcohols, such as methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-methyl-1-propanol, 1-pentanol, 2-pentanol, 3-pentanol,2-methyl-1-butanol, 1-methyl-1-butanol, 3-methyl-1-butanol,1-methyl-1-pentanol, 2-methyl-1-pentanol, 3-methyl-1-pentanol,t-butanol, cyclohexanol, 2-ethyl-1-butanol, and mixtures thereof,preferably methanol, ethanol, 1-propanol, 2-propanol, 1-butanol,2-methyl-1-propanol, t-butanol, and mixtures thereof. One highlypreferred copolymer contains acrylic acid and t-butyl acrylate monomericunits, preferably with acrylic acid/t-butyl acrylate ratios of fromabout 90:10 to about 10:90, preferably from about 70:30 to about 15:85,more preferably from about 40:60 to about 20:80. Nonlimiting examples ofacrylic acid/tert-butyl acrylate copolymers useful in the presentinvention are those typically with a molecular weight of from about1,000 to about 2,000,000, preferably from about 5,000 to about1,000,000, and more preferably from about 30,000 to about 300,000, andwith an approximate acrylic acid/tert-butyl acrylate weight ratio ofabout 25:75 and an average molecular weight of from about 70,000 toabout 100,000, and those with an approximate acrylic acid/tert-butylacrylate weight ratio of about 35:65 and an average molecular weight offrom about 60,000 to about 90,000.

The film-forming and/or adhesive polymer of the present invention ispresent at least an effective amount to provide shape retention,typically from about 0.05% to about 10%, preferably from about 0.1% toabout 5%, more preferably from about 0.2% to about 3%, even morepreferably from about 0.3% to about 1.5%, by weight of the usagecomposition.

The adhesive polymer is present in the composition in a sufficientamount to result in an amount of from about 0.001% to about 1%,preferably from about 0.01% to about 0.5%, more preferably from about0.02% to about 0.4% by weight of polymer per weight of dry fabrics.

It is not intended to exclude the use of higher or lower levels of thepolymers, as long as an effective amount is used to provide adhesive andfilm-forming properties to the composition and the composition can beformulated and effectively applied for its intended purpose.

Silicones and film-forming polymers can be combined to produce preferredwrinkle reducing actives. Typically the weight ratio of silicone tofilm-forming polymer from about 10:1 to about 1:10, preferably fromabout 5:1 to about 1:5, and more preferably from about 2:1 to about 1:2.Typically, the preferred wrinkle reducing active of silicone pluspolymer is present at a level of from about 0.1% to about 8%, preferablyfrom about 0.3% to about 5%, more preferably from about 0.5% to about3%, by weight of the composition.

Optional but preferred adhesive and/or film forming polymers that areuseful in the composition of the present invention actually containsilicone moieties in the polymers themselves. These preferred polymersinclude graft and block copolymers of silicone with moieties containinghydrophilic and/or hydrophobic monomers described hereinbefore. Thesilicone-containing copolymers in the spray composition of the presentinvention provide shape retention, body, and/or good, soft fabric feel.Highly preferred silicone-containing copolymers contain hydrophobicmonomers and hydrophilic monomers which comprise unsaturated organicmono-carboxylic and/or polycarboxylic acid monomers, such as acrylicacid, methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and salts thereof, and mixtures thereof, and optionallyother hydrophilic monomers.

Both silicone-containing graft and block copolymers useful in thepresent invention have the following properties:

-   -   (1) the silicone portion is covalently attached to the        non-silicone portion;    -   (2) the molecular weight of the silicone portion is from about        1,000 to about 50,000; and    -   (3) the non-silicone portion must render the entire copolymer        soluble or dispersible in the wrinkle control composition        vehicle and permit the copolymer to deposit on/adhere to the        treated fabrics.

Suitable silicone copolymers include the following:

-   -   (a) Silicone Graft Copolymers

Preferred silicone-containing polymers are the silicone graft copolymerscomprising acrylate groups described, along with methods of making them,in U.S. Pat. No. 5,658,557, Bolich et al., issued Aug. 19, 1997, U.S.Pat. No. 4,693,935, Mazurek, issued Sep. 15, 1987, and U.S. Pat. No.4,728,571, Clemens et al., issued Mar. 1, 1988. Additionalsilicone-containing polymers are disclosed in U.S. Pat. No. 5,480,634,Hayama et al, issued Oct. 2, 1996, U.S. Pat. No. 5,166,276, Hayama etal., issued Nov. 24, 1992, U.S. Pat. No. 5,061,481, issued Oct. 29,1991, Suzuki et al., U.S. Pat. No. 5,106,609, Bolich et al., issued Apr.21, 1992, U.S. Pat. No. 5,100,658, Bolich et al., issued Mar. 31, 1992,U.S. Pat. No. 5,100,657, Ansher-Jackson, et al., issued Mar. 31, 1992,U.S. Pat. No. 5,104,646, Bolich et al., issued Apr. 14, 1992, all ofwhich are incorporated herein by reference.

These polymers preferably include copolymers having a vinyl polymericbackbone having grafted onto it monovalent siloxane polymeric moieties,and components consisting of non-silicone hydrophilic and hydrophobicmonomers.

The silicone-containing monomers are exemplified by the general formula:X(Y)_(n)Si(R)_(3-m)Z_(m)wherein X is a polymerizable group, such as a vinyl group, which is partof the backbone of the polymer; Y is a divalent linking group; R is ahydrogen, hydroxyl, lower alkyl (e.g. C₁–C₄), aryl, alkaryl, alkoxy, oralkylamino; Z is a monovalent polymeric siloxane moiety having anaverage molecular weight of at least about 500, is essentiallyunreactive under copolymerization conditions, and is pendant from thevinyl polymeric backbone described above; n is 0 or 1; and m is aninteger from 1 to 3.

The preferred silicone-containing monomer has a weight average molecularweight of from about 1,000 to about 50,000, preferably from about 3,000to about 40,000, most preferably from about 5,000 to about 20,000.

Nonlimiting examples of preferred silicone-containing monomers have thefollowing formulas:

In these structures m is an integer from 1 to 3, preferably 1; p is 0 or1; q is an integer from 2 to 6; n is an integer from 0 to 4, preferably0 or 1, more preferably 0; R¹ is hydrogen, lower alkyl, alkoxy,hydroxyl, aryl, alkylamino, preferably R¹ is alkyl; R″ is alkyl orhydrogen; X isCH(R³)═C(R⁴)—R³ is hydrogen or —COOH, preferably hydrogen; R⁴ is hydrogen, methyl or—CH₂COOH, preferably methyl; Z isR⁵—[Si(R⁶)(R⁷)—O—]_(r)wherein R⁵, R⁶, and R⁷, independently are lower alkyl, alkoxy,alkylamino, hydrogen or hydroxyl, preferably alkyl; and r is an integerof from about 10 to about 700, preferably from about 40 to about 600,more preferably from about 70 to about 300. Most preferably, R⁵, R⁶, andR⁷ are methyl, p=0, and q=3.

Silicone-containing adhesive and/or film-forming copolymers useful inthe present invention comprise from 0% to about 90%, preferably fromabout 10% to about 80%, more preferably from about 40% to about 75% ofhydrophobic monomer, from about 0% to about 90%, preferably from about5% to about 80% of hydrophilic monomer, and from about 5% to about 50%,preferably from about 10% to about 40%, more preferably from about 15%to about 25% of silicone-containing monomer.

The composition of any particular copolymer will help determine itsformulation properties. In fact, by appropriate selection andcombination of particular hydrophobic, hydrophilic andsilicone-containing components, the copolymer can be optimized forinclusion in specific vehicles. For example, polymers which are solublein an aqueous formulation preferably contain from 0% to about 70%,preferably from about 5% to about 70% of hydrophobic monomer, and fromabout 30% to about 98%, preferably from about 30% to about 80%, ofhydrophilic monomer, and from about 1% to about 40% ofsilicone-containing monomer. Polymers which are dispersible preferablycontain from 0% to about 70%, more preferably from about 5% to about70%, of hydrophobic monomer, and from about 20% to about 80%, morepreferably from about 20% to about 60%, of hydrophilic monomer, and fromabout 1% to about 40% of silicone-containing monomer.

The silicone-containing copolymers preferably have a weight averagemolecular weight of from about 10,000 to about 1,000,000, preferablyfrom about 30,000 to about 300,000.

The preferred polymers comprise a vinyl polymeric backbone, preferablyhaving a Tg or a Tm as defined above of about −20° C. and, grafted tothe backbone, a polydimethylsiloxane macromer having a weight averagemolecular weight of from about 1,000 to about 50,000, preferably fromabout 5,000 to about 40,000, most preferably from about 7,000 to about20,000. The polymer is such that when it is formulated into the finishedcomposition, and then dried, the polymer phase separates into adiscontinuous phase which includes the polydimethylsiloxane macromer anda continuous phase which includes the backbone. Exemplary siliconegrafted polymers for use in the present invention include the following,where the composition of the copolymer is given with the approximateweight percentage of each monomer used in the polymerization reaction toprepare the copolymer: N,N-dimethylacrylamide/isobutylmethacrylate/(PDMS macromer —20,000 approximate molecular weight)(PDMSis polydimethylsiloxane) (20/60/20 w/w/w), copolymer of averagemolecular weight of about 400,000; N,N-dimethylacrylamide/(PDMS macromer—20,000 approximate molecular weight) (80/20 w/w), copolymer of averagemolecular weight of about 300,000;t-butylacrylate/N,N-dimethylacrylamide/(PDMS macromer —10,000approximate molecular weight) (70/10/20), copolymer of average molecularweight of about 400,000; and (N,N,N-trimethylammonioethylmethacrylatechloride)/N,N-dimethylacrylamide/(PDMS macromer —15,000 approximatemolecular weight) (40/40/20), copolymer of average molecular weight ofabout 150,000.

Highly preferred adjunct shape retention copolymers of this type containhydrophobic monomers, silicone-containing monomers and hydrophilicmonomers which comprise unsaturated organic mono- and polycarboxylicacid monomers, such as acrylic acid, methacrylic acid, crotonic acid,maleic acid and its half esters, itaconic acid, and salts thereof, andmixtures thereof. A highly preferred copolymer is composed of acrylicacid, t-butyl acrylate and silicone-containing monomeric units,preferably with from about 20% to about 90%, preferably from about 30%to about 80%, more preferably from about 50% to about 75% t-butylacrylate; from about 5% to about 60%, preferably from about 8% to about45%, more preferably from about 10% to about 30% of acrylic acid; andfrom about 5% to about 50%, preferably from about 7% to about 40%, morepreferably from about 10% to about 30% of polydimethylsiloxane of anaverage molecular weight of from about 1,000 to about 50,000, preferablyfrom about 5,000 to about 40,000, most preferably from about 7,000 toabout 20,000. Nonlimiting examples of acrylic acid/tert-butylacrylate/polydimethyl siloxane macromer copolymers useful in the presentinvention, with approximate monomer weight ratio, are:t-butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 10,000approximate molecular weight) (70/10/20 w/w/w), copolymer of averagemolecular weight of about 300,000; t-butylacrylate/acrylicacid/(polydimethylsiloxane macromer, 10,000 approximate molecularweight) (65/25/10 w/w/w), copolymer of average molecular weight of about200,000; t-butyl acrylate/acrylic acid/(polydimethylsiloxane macromer,10,000 approximate molecular weight) (63/20/17), copolymer of averagemolecular weight of from about 120,000 to about 150,000; andn-butylmethacrylate/acrylic acid/(polydimethylsiloxane macromer —20,000approximate molecular weight) (70/10/20 w/w/w), copolymer of averagemolecular weight of about 100,000. A useful copolymer of this type isDiahold® ME from Mitsubishi Chemical Corp., which is a t-butylacrylate/acrylic acid/(polydimethylsiloxane macromer, 12,000 approximatemolecular weight) (60/20/20), copolymer of average molecular weight ofabout 128,000.

(b) Silicone Block Copolymers

Also useful herein are silicone block copolymers comprising repeatingblock units of polysiloxanes.

Examples of silicone-containing block copolymers are found in U.S. Pat.No. 5,523,365, to Geck et al., issued Jun. 4, 1996; U.S. Pat. No.4,689,289, to Crivello, issued Aug. 25, 1987; U.S. Pat. No. 4,584,356,to Crivello, issued Apr. 22, 1986; Macromolecular Design, Concept &Practice, Ed: M. K. Mishra, Polymer Frontiers International, Inc.,Hopewell Jct., NY (1994), and Block Copolymers, A. Noshay and J. E.McGrath, Academic Press, NY (1977), which are all incorporated byreference herein in their entirety. Other silicone block copolymerssuitable for use herein are those described, along with methods ofmaking them, in the above referenced and incorporated U.S. Pat. No.5,658,577.

The silicone-containing block copolymers useful in the present inventioncan be described by the formulas A—B, A—B—A, and —(A⁻ B)_(n)— wherein nis an integer of 2 or greater. A—B represents a diblock structure, A—B—Arepresents a triblock structure, and —(A—B)_(n)— represents a multiblockstructure. The block copolymers can comprise mixtures of diblocks,triblocks, and higher multiblock combinations as well as small amountsof homopolymers.

The silicone block portion, B, can be represented by the followingpolymeric structure—(SiR₂O)_(m)—,wherein each R is independently selected from the group consisting ofhydrogen, hydroxyl, C₁–C₆ alkyl, C₁–C₆ alkoxy, C₂–C₆ alkylamino, styryl,phenyl, C₁–C₆ alkyl or alkoxy-substituted phenyl, preferably methyl; andm is an integer of about 10 or greater, preferably of about 40 orgreater, more preferably of about 60 or greater, and most preferably ofabout 100 or greater.

The non-silicone block, A, comprises monomers selected from the monomersas described hereinabove in reference to the non-silicone hydrophilicand hydrophobic monomers for the silicone grafted copolymers. Vinylblocks are preferred co-monomers. The block copolymers preferablycontain one or more non-silicone blocks, and up to about 50%, preferablyfrom about 10% to about 20%, by weight of one or more polydimethylsiloxane blocks.

(c) Sulfur-Linked Silicone-Containing Copolymers

Also useful herein are sulfur-linked silicone containing copolymers,including block copolymers. As used herein in reference to siliconecontaining copolymers, the term “sulfur-linked” means that the copolymercontains a sulfur linkage (i.e., —S—), a disulfide linkage (i.e.,—S—S—), or a sulfhydryl group (i.e., —SH).

These sulfur-linked silicone-containing copolymers are represented bythe following general formula:

wherein

-   -   each G₅ and G₆ is independently selected from the group        consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,        fluoroalkyl, hydrogen, and —ZSA, wherein A represents a vinyl        polymeric segment consisting essentially of polymerized free        radically polymerizable monomer, and Z is a divalent linking        group (Useful divalent linking groups Z include but are not        limited to the following: C₁ to C₁₀ alkylene, alkarylene,        arylene, and alkoxyalkylene. Preferably, Z is selected from the        group consisting of methylene and propylene for reasons of        commercial availability.);    -   each G₂ comprises A;    -   each G₄ comprises A;    -   each R₁ is a monovalent moiety selected from the group        consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,        fluoroalkyl, hydrogen, and hydroxyl (Preferably, R₁ represents        monovalent moieties which can independently be the same or        different selected from the group consisting of C₁₋₄ alkyl and        hydroxyl for reasons of commercial availability. Most        preferably, R₁ is methyl.);    -   each R₂ is a divalent linking group (Suitable divalent linking        groups include but are not limited to the following: C₁ to C₁₀        alkylene, arylene, alkarylene, and alkoxyalkylene. Preferably,        R₂ is selected from the group consisting of C₁₋₃ alkylene and        C₇–C₁₀ alkarylene due to ease of synthesis of the compound. Most        preferably, R₂ is selected from the group consisting of —CH₂—,        1,3-propylene, and        each R₃ represents monovalent moieties which can independently        be the same or different and are selected from the group        consisting of alkyl, aryl, alkaryl, alkoxy, alkylamino,        fluoroalkyl, hydrogen, and hydroxyl (Preferably, R₃ represents        monovalent moieties which can independently be the same or        different selected from the group consisting of C₁₋₄ alkyl and        hydroxyl for reasons of commercial availability. Most        preferably, R₃ is methyl.);    -   each R₄ is a divalent linking group (Suitable divalent linking        groups include but are not limited to the following: C₁ to C₁₀        alkylene, arylene, alkarylene, and alkoxyalkylene. Preferably,        R₄ is selected from the group consisting of C₁₋₃ alkylene and        C₇–C₁₀ alkarylene for ease of synthesis. Most preferably, R₄ is        selected from the group consisting of —CH₂—, 1,3-propylene, and    -   x is an integer of 0–3;    -   y is an integer of 5 or greater (preferably y is an integer        ranging from about 14 to about 700, preferably from about 20 to        about 200); and    -   q is an integer of 0–3;        wherein at least one of the following is true:    -   q is an integer of at least 1;    -   x is an integer of at least 1;    -   G₅ comprises at least one —ZSA moiety; or    -   G₆ comprises at least one —ZSA moiety.

As noted above, A is a vinyl polymeric segment formed from polymerizedfree radically polymerizable monomers. The selection of A is typicallybased upon the intended uses of the composition, and the properties thecopolymer must possess in order to accomplish its intended purpose. If Acomprises a block in the case of block copolymers, a polymer having ABand/or ABA architecture will be obtained depending upon whether amercapto functional group —SH is attached to one or both terminalsilicon atoms of the mercapto functional silicone compounds,respectively. The weight ratio of vinyl polymer block or segment, tosilicone segment of the copolymer can vary. The preferred copolymers arethose wherein the weight ratio of vinyl polymer segment to siliconesegment ranges from about 98:2 to 50:50, in order that the copolymerpossesses properties inherent to each of the different polymericsegments while retaining the overall polymer's solubility.

Sulfur linked silicone copolymers are described in more detail in U.S.Pat. No. 5,468,477, to Kumar et al., issued Nov. 21, 1995, and PCTApplication No. WO 95/03776, assigned to 3M, published Feb. 9, 1995,which are incorporated by reference herein in their entirety.

Other useful silicone-containing polymers are those containinghydrophilic portions, such as polyvinylpyrrolidone/quaternaries,polyacrylates, polyacrylamides, polysulfonates, and mixtures thereof,and are disclosed, e.g., in U.S. Pat. No. 5,120,812, incorporated hereinby reference.

The film-forming and/or adhesive silicone-containing copolymer of thepresent invention is present at least an effective amount to provideshape retention, typically from about 0.05% to about 10%, preferablyfrom about 0.1% to about 5%, more preferably from about 0.2% to about3%, even more preferably from about 0.3% to about 1.5%, by weight of theusage composition.

The silicone-containing copolymer is present in the composition in asufficient amount to result in an amount of from about 0.001% to about1%, preferably from about 0.01% to about 0.5%, more preferably fromabout 0.02% to about 0.4% by weight of polymer per weight of dryfabrics.

When the optional cyclodextrin is present in the composition, thepolymer useful in providing shape retention in the composition of thepresent invention should be cyclodextrin-compatible, that is it shouldnot substantially form complexes with cyclodextrin so as to diminishperformance of the cyclodextrin and/or the polymer. Complex formationaffects both the ability of the cyclodextrin to absorb odors and theability of the polymer to impart shape retention to fabric. In thiscase, the monomers having pendant groups that can complex withcyclodextrin are not preferred because they can form complexes withcyclodextrin. Examples of such monomers are acrylic or methacrylic acidesters of C₇–C₁₈ alcohols, such as neodecanol, 3-heptanol, benzylalcohol, 2-octanol, 6-methyl-1-heptanol, 2-ethyl-1-hexanol,3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol, and 1-decanol;aromatic vinyls, such as styrene; t-butylstyrene; vinyl toluene; and thelike.

Starch

Starch is not normally preferred, since it makes the fabric resistant todeformation. However, it does provide increased “body” which is oftendesired. Starch is particularly preferred in compositions of thisinvention to be used with ironing. When used, starch is solubilized ordispersed in the composition. Any type of starch, e.g. those derivedfrom corn, wheat, rice, grain sorghum, waxy grain sorghum, waxy maize ortapioca, or mixtures thereof and water soluble or dispersiblemodifications or derivatives thereof, can be used in the composition ofthe present invention. Low viscosity commercially available propoxylatedand/or ethoxylated starches are useable in the present composition andare preferred since their low viscosity at relatively high solidsconcentrations make them very adaptable to spraying processes. Suitablealkoxylated, low viscosity starches are submicron sized particles ofhydrophobic starch that are readily dispersed in water and are preparedby alkoxylation of granular starch with a monofunctional alkoxylatingagent which provides the starch with ether linked hydrophilic groups. Asuitable method for their preparation is taught in U.S. Pat. No.3,462,283. In accordance with the invention, the propoxylated orethoxylated starch derivatives are dispersed in the aqueous medium in anamount of from about 0.1% to about 10%, preferably from about 0.5% toabout 6%, more preferably from about 1% to about 4% by weight of theusage composition.

Lithium Salts.

Optional lithium salts are useful in the fabric care compositions of thepresent invention for providing improved fabric wrinkle control.Nonlimiting examples of lithium salts that are useful in the presentinvention are lithium bromide, lithium chloride, lithium lactate,lithium benzoate, lithium acetate, lithium sulfate, lithium tartrate,and/or lithium bitartrate, preferably lithium bromide and/or lithiumlactate. Some water soluble salts such as, lithium benzoate are notpreferred when the optional cyclodextrin is present because they canform complexes with cyclodextrin. Useful levels of lithium salts arefrom about 0.1% to about 10%, preferably from about 0.5% to about 7%,more preferably from about 1% to about 5%, by weight of the usagecomposition.

Hydrophilic Plasticizer

Optionally, the composition can contain a hydrophilic plasticizer tosoften both the fabric fibers, especially cotton fibers, and the adjunctadhesive and/or film-forming shape retention polymers. Examples of thepreferred hydrophilic plasticizers are short chain low molecular weightpolyhydric alcohols, such as is glycerol, ethylene glycol, propyleneglycol, diethylene glycol, dipropylene glycol, sorbitol, erythritol ormixtures thereof, more preferably diethylene glycol, dipropylene glycol,ethylene glycol, propylene glycol and mixtures thereof. When ahydrophilic plasticizer is used, it is present in the at a level of from0.01% to 5%, preferably from 0.05% to 2%, more preferably from 0.1% to1% by weight of the usage composition.

Surfactant

Surfactant is an optional but highly preferred ingredient of the presentinvention. Surfactant is especially useful in the composition tofacilitate the dispersion and/or solubilization of wrinkle controlagents such as silicones and/or certain relatively water insolubleadjunct shape retention polymers. The surfactant can provide someplasticizing effect to the adjunct shape retention polymers resulting ina more flexible polymer network. Such surfactant is preferably includedwhen the composition is used in a spray dispenser in order to enhancethe spray characteristics of the composition and allow the composition,including the fabric care polysaccharide with globular structure, todistribute more evenly, and to prevent clogging of the spray apparatus.The spreading of the composition can also allow it to dry faster, sothat the treated material is ready to use sooner. For concentratedcompositions, the surfactant facilitates the dispersion of many activessuch as antimicrobial actives and perfumes in the concentrated aqueouscompositions. Suitable surfactant useful in the present invention isnonionic surfactant, anionic surfactant, cationic surfactant, amphotericsurfactant, and mixtures thereof. When surfactant is used in thecomposition of the present invention, it is added at an effective amountto provide one, or more of the benefits described herein, typically fromabout 0.01% to about 5%, preferably from about 0.05% to about 3%, morepreferably from about 0.1% to about 2%, and even more preferably, fromabout 0.2% to about 1%, by weight of the usage composition.

A preferred type of surfactant is ethoxylated surfactant, such asaddition products of ethylene oxide with fatty alcohols, fatty acids,fatty amines, etc. Optionally, addition products of mixtures of ethyleneoxide and propylene oxide with fatty alcohols, fatty acids, fatty aminescan be used. The ethoxylated surfactant includes compounds having thegeneral formula:R⁸—Z—(CH₂CH₂O)_(S)Bwherein R⁸ is an alkyl group or an alkyl aryl group, selected from thegroup consisting of primary, secondary and branched chain alkylhydrocarbyl groups, primary, secondary and branched chain alkenylhydrocarbyl groups, and/or primary, secondary and branched chain alkyl-and alkenyl-substituted phenolic hydrocarbyl groups having from about 6to about 20 carbon atoms, preferably from about 8 to about 18, morepreferably from about 10 to about 15 carbon atoms; s is an integer fromabout 2 to about 45, preferably from about 2 to about 20, morepreferably from about 2 to about 15; B is a hydrogen, a carboxylategroup, or a sulfate group; and linking group Z is —O—, —C(O)O—,—C(O)N(R)—, or —C(O)N(R)—, and mixtures thereof, in which R, whenpresent, is R⁸ or hydrogen.

The nonionic surfactants herein are characterized by an HLB(hydrophilic-lipophilic balance) of from 5 to 20, preferably from 6 to15.

Nonlimiting examples of preferred ethoxylated surfactant are:

-   -   straight-chain, primary alcohol ethoxylates, with R⁸ being        C₈–C₁₈ alkyl and/or alkenyl group, more preferably C₁₀–C ₁₄, and        s being from about 2 to about 8, preferably from about 2 to        about 6;    -   straight-chain, secondary alcohol ethoxylates, with R⁸ being        C₈–C₁₈ alkyl and/or alkenyl, e.g., 3-hexadecyl, 2-octadecyl,        4-eicosanyl, and 5-eicosanyl, and s being from about 2 to about        10;    -   alkyl phenol ethoxylates wherein the alkyl phenols having an        alkyl or alkenyl group containing from 3 to 20 carbon atoms in a        primary, secondary or branched chain configuration, preferably        from 6 to 12 carbon atoms, and s is from about 2 to about 12,        preferably from about 2 to about 8;    -   branched chain alcohol ethoxylates, wherein branched chain        primary and secondary alcohols (or Guerbet alcohols) which are        available, e.g., from the well-known “OXO” process or        modification thereof are ethoxylated.

Especially preferred are alkyl ethoxylate surfactants with each R⁸ beingC₈–C₁₆ straight chain and/or branch chain alkyl and the number ofethyleneoxy groups s being from about 2 to about 6, preferably fromabout 2 to about 4, more preferably with R⁸ being C₈–C₁₅ alkyl and sbeing from about 2.25 to about 3.5. These nonionic surfactants arecharacterized by an HLB of from 6 to about 11, preferably from about 6.5to about 9.5, and more preferably from about 7 to about 9. Nonlimitingexamples of commercially available preferred surfactants are Neodol91-2.5 (C₉–C₁₀, s=2.7, HLB=8.5), Neodol 23-3 (C₁₂–C₁₃, s=2.9, HLB=7.9)and Neodol 25-3 (C₁₂–C₁₅, s=2.8, HLB=7.5). It is found, verysurprisingly, that these preferred surfactants which are themselves notvery water soluble (0.1% aqueous solutions of these surfactants are notclear), can at low levels, effectively dissolve and/or disperse adjunctshape retention polymers such as copolymers containing acrylic acid andtert-butyl acrylate and silicone-containing copolymers into clearcompositions, even without the presence of a low molecular weightalcohol.

Also preferred is a nonionic surfactant selected from the groupconsisting of fatty acid (C₁₂₋₁₈) esters of ethoxylated (EO₅₋₁₀₀)sorbitans. More preferably said surfactant is selected from the groupconsisting of mixtures of laurate esters of sorbitol and sorbitolanhydrides; mixtures of stearate esters of sorbitol and sorbitolanhydrides; and mixtures of oleate esters of sorbitol and sorbitolanhydrides. Even more preferably said surfactant is selected from thegroup consisting of Polysorbite 20, which is a mixture of laurate estersof sorbitol and sorbitol anhydrides consisting predominantly of themonoester, condensed with about 20 moles of ethylene oxide; Polysorbate60 which is a mixture of stearate esters of sorbitol and sorbitolanhydride, consisting predominantly of the monoester, condensed withabout 20 moles of ethylene oxide; Polysorbate 80 which is a mixture ofoleate esters of sorbitol and sorbitol anhydrides, consistingpredominantly of the monoester, condensed with about 20 moles ofethylene oxide; and mixtures thereof. Most preferably, said surfactantis Polysorbate 60.

Other examples of preferred ethoxylated surfactant include carboxylatedalcohol ethoxylate, also known as ether carboxylate, with R⁸ having fromabout 12 to about 16 carbon atoms and s being from about 5 to about 13;ethoxylated quaternary ammonium surfactants, such as PEG-5 cocomoniummethosulfate, PEG-15 cocomonium chloride, PEG-15 oleammonium chlorideand bis(polyethoxyethanol)tallow ammonium chloride.

Other suitable nonionic ethoxylated surfactants are ethoxylated alkylamines derived from the condensation of ethylene oxide with hydrophobicalkyl amines, with R⁸ having from about 8 to about 22 carbon atoms and sbeing from about 3 to about 30.

Also suitable nonionic ethoxylated surfactants for use herein arealkylpolysaccharides which are disclosed in U.S. Pat. No. 4,565,647,Llenado, issued Jan. 21, 1986, having a hydrophobic group containingfrom about 8 to about 30 carbon atoms, preferably from about 10 to about16 carbon atoms and a polysaccharide, e.g., a polyglycoside, hydrophilicgroup containing from about 1.3 to about 10, preferably from about 1.3to about 3, most preferably from about 1.3 to about 2.7 saccharideunits. Any reducing saccharide containing 5 or 6 carbon atoms can beused, e.g., glucose, galactose and galactosyl moieties can besubstituted for the glucosyl moieties. The intersaccharide bonds can be,e.g., between the one position of the additional saccharide units andthe 2-, 3-, 4-, and/or 6-positions on the preceding saccharide units.The preferred alkylpolyglycosides have the formulaR²O(C_(n)H_(2n)O)t(glycosyl)_(x)wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from 10 to 18, preferably from 12 to 14, carbonatoms; n is 2 or 3, preferably from about 1.3 to about 3, mostpreferably from about 1.3 to about 2.7. The glycosyl is preferablyderived from glucose.

Another class of preferred surfactants that are useful in theformulation of the compositions of the present invention, to solubilizeand/or disperse silicone lubricants and/or silicone-containing adjunctshape retention copolymers, are silicone surfactants. They can be usedalone and/or preferably in combination with the preferred alkylethoxylate surfactants described herein above. Nonlimiting examples ofsilicone surfactants are the polyalkylene oxide polysiloxanes having adimethyl polysiloxane hydrophobic moiety and one or more hydrophilicpolyalkylene side chains, and having the general formula:R¹—(CH₃)₂SiO—[(CH₃)₂SiO]_(a)—[(CH₃)(R¹)SiO]_(b)—Si(CH₃)₂—R¹wherein a+b are from about 1 to about 50, preferably from about 3 toabout 30, more preferably from about 10 to about 25, and each R¹ is thesame or different and is selected from the group consisting of methyland a poly(ethyleneoxide/propyleneoxide) copolymer group having thegeneral formula:—(CH₂)_(n) O(C₂H₄O)_(c)(C₃H₆O)_(d)R²with at least one R¹ being a poly(ethyleneoxy/propyleneoxy) copolymergroup, and wherein n is 3 or 4, preferably 3; total c (for allpolyalkyleneoxy side groups) has a value of from 1 to about 100,preferably from about 6 to about 100; total d is from 0 to about 14,preferably from 0 to about 3; and more preferably d is 0; total c+d hasa value of from about 5 to about 150, preferably from about 9 to about100 and each R² is the same or different and is selected from the groupconsisting of hydrogen, an alkyl having 1 to 4 carbon atoms, and anacetyl group, preferably hydrogen and methyl group. Each polyalkyleneoxide polysiloxane has at least one R¹ group being apoly(ethyleneoxide/propyleneoxide) copolymer group.

Nonlimiting examples of this type of surfactants are the Silwet®surfactants which are available OSi Specialties, Inc., Danbury, Conn.Representative Silwet surfactants which contain only ethyleneoxy (C₂H₄O)groups are as follows.

Name Average MW Average a + b Average total c L-7608 600 1 9 L-76071,000 2 17 L-77  600 1 9 L-7605 6,000 20 99 L-7604 4,000 21 53 L-76004,000 11 68 L-7657 5,000 20 76 L-7602 3,000 20 29 L-7622 10,000 88 75

Nonlimiting examples of surfactants which contain both ethyleneoxy (C₂H₄0) and propyleneoxy (C₃H₆ 0) groups are as follows.

Name Average MW EO/PO ratio Silwet L-720 12,000 50/50 Silwet L-700120,000 40/60 Silwet L-7002  8,000 50/50 Silwet L-7210 13,000 20/80Silwet L-7200 19,000 75/25 Silwet L-7220 17,000 20/80

The molecular weight of the polyalkyleneoxy group (R¹) is less than orequal to about 10,000. Preferably, the molecular weight of thepolyalkyleneoxy group is less than or equal to about 8,000, and mostpreferably ranges from about 300 to about 5,000. Thus, the values of cand d can be those numbers which provide molecular weights within theseranges. However, the number of ethyleneoxy units (—C₂H₄O) in thepolyether chain (R¹) must be sufficient to render the polyalkylene oxidepolysiloxane water dispersible or water soluble. If propyleneoxy groupsare present in the polyalkylenoxy chain, they can be distributedrandomly in the chain or exist as blocks. Surfactants which contain onlypropyleneoxy groups without ethyleneoxy groups are not preferred.Preferred Silwet surfactants are L-7600, L-7602, L-7604, L-7605, L-7657,and mixtures thereof. The most preferred Silwet surfactant forsolubilizing and/or dispersing the adjunct silicone-containing shaperetention polymers and/or the volatile silicone is the low molecularweight L-77. Besides surface activity, polyalkylene oxide polysiloxanesurfactants can also provide other benefits, such as antistaticbenefits, lubricity and softness to fabrics.

Other useful silicone surfactants are those having a hydrophobic moietyand hydrophilic ionic groups, including, e.g., anionic, cationic, andamphoteric groups. Nonlimiting examples of anionic silicone surfactantsare silicone sulfosuccinates, silicone sulfates, silicone phosphates,silicone carboxylates, and mixtures thereof, as disclosed respectivelyin U.S. Pat. Nos. 4,717,498, 4,960,845, 5,149,765, and 5,296,434.Nonlimiting examples of cationic silicone surfactants are silicone alkylquats (quaternary ammoniums), silicone amido quats, silicone imidazolinequats, and mixtures thereof, as disclosed respectively in U.S. Pat. Nos.5,098,979, 5,135,294, and 5,196,499. Nonlimiting examples of amphotericsilicone surfactants are silicone betaines, silicone amino proprionates,silicone phosphobetaines, and mixtures thereof, as disclosedrespectively in U.S. Pat. Nos. 4,654,161, 5,073,619, and 5,237,035. Allof these patents are incorporated herein by reference.

Fabric care composition of the present invention to be used in the washcycle can be either used along with a general laundry detergent oractually a detergent composition comprising a fabric care polysaccharidewith globular structure. The detergent compositions according to thepresent invention comprise a surfactant or surfactant system wherein thesurfactant can be selected from nonionic and/or anionic and/or cationicand/or ampholytic and/or zwitterionic and/or semi-polar nonionicsurfactants.

The surfactant is typically present at a level of from 0.1% to 60% byweight. More preferred levels of incorporation are 1% to 35% by weight,most preferably from 1% to 30% by weight of detergent compositions inaccord with the invention.

The surfactant is preferably formulated to be compatible with the fabriccare polysaccharide with globular structure present in the composition.

Examples of suitable nonionic, anionic, cationic, ampholytic,zwitterionic and semi-polar nonionic surfactants are disclosed in U.S.Pat. Nos. 5,707,950 and 5,576,282, incorporated herein by reference.

Highly preferred nonionic surfactants are polyhydroxy fatty acid amidesurfactants of the formula:R²—C(O)—N(R¹)—Z,wherein R¹ is H, or R¹ is C₁₋₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl or a mixture thereof, R² is C₅₋₃₁ hydrocarbyl, and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivativethereof. Preferably, R¹ is methyl, R² is a straight C₁₁₋₁₅ alkyl orC₁₆₋₁₈ alkyl or alkenyl chain such as coconut alkyl or mixtures thereof,and Z is derived from a reducing sugar such as glucose, fructose,maltose, lactose, in a reductive amination reaction.

Highly preferred anionic surfactants include alkyl alkoxylated sulfatesurfactants hereof are water soluble salts or acids of the formulaRO(A)_(m)SO3M wherein R is an unsubstituted C₁₂–C₂₄ alkyl orhydroxyalkyl group having a C₁₀–C₂₄ alkyl component, preferably aC₁₂–C₂₀ alkyl or hydroxyalkyl, more preferably C₁₂–C₁₈ alkyl orhydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero,typically between about 0.5 and about 6, more preferably between about0.5 and about 3, and M is H or a cation which can be, for example, ametal cation (e.g., sodium, potassium, lithium, calcium, magnesium,etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylatedsulfates as well as alkyl propoxylated sulfates are contemplated herein.

When included therein, the laundry detergent compositions of the presentinvention typically comprise from about 1% to about 40%, preferably fromabout 3% to about 20% by weight of such anionic surfactants.

The above individual Compounds (actives) can be used individually or asmixtures.

One type of optional but highly desirable cationic compound which can beused in combination with the above softening actives are compoundscontaining one long chain acyclic C₈–C₂₂ hydrocarbon group, selectedfrom the group consisting of: wherein R⁷ is hydrogen or a C₁–C₄saturated alkyl or hydroxyalkyl group, and R¹ and A⁻ are defined asherein above;

-   -   (12) Acyclic quaternary ammonium salts having the formula:        [R¹—N(R⁵)₂—R⁶]⁺A⁻        wherein R⁵ and R⁶ are C₁–C₄ alkyl or hydroxyalkyl groups, and R¹        and A⁻ are defined as herein above;    -   (13) Substituted imidazolinium salts having the formula:        wherein R⁷ is hydrogen or a C₁–C₄ saturated alkyl or        hydroxyalkyl group, and R¹ and A⁻ are defined as hereinabove;    -   (14) Substituted imidazolinium salts having the formula:        wherein R⁵ is a C₁–C₄ alkyl or hydroxyalkyl group, and R¹, R²,        and A⁻ are as defined above;    -   (15) Alkylpyridinium salts having the formula:        wherein R⁴ is an acyclic aliphatic C₈–C₂₂ hydrocarbon group and        A⁻ is an anion;    -   (16) Alkanamide alkylene pyridinium salts having the formula:

Highly preferred cationic surfactants are the water-soluble quaternaryammonium compounds useful in the present composition having the formula:R₁R₂R₃R₄N⁺X⁻wherein R₁ is C₈–C₁₆ alkyl, each of R₂, R₃ and R₄ is independentlyC_(1–C) ₄ alkyl, C₁–C₄ hydroxy alkyl, benzyl, and —(C₂H₄₀)_(x)H where xhas a value from 2 to 5, and X is an anion. Not more than one of R₂, R₃or R₄ should be benzyl.

When included therein, the detergent compositions of the presentinvention typically comprise from 0.2% to about 25%, preferably fromabout 1% to about 8% by weight of such cationic surfactants.

When included therein, the detergent compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such ampholytic surfactants.

When included therein, the detergent compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such zwitterionic surfactants.

When included therein, the detergent compositions of the presentinvention typically comprise from 0.2% to about 15%, preferably fromabout 1% to about 10% by weight of such semi-polar nonionic surfactants.

The detergent composition of the present invention can further comprisea cosurfactant selected from the group of primary or tertiary amines.

Suitable primary amines for use herein include amines according to theformula R₁NH₂ wherein R₁ is a C₆–C₁₂, preferably C₆–C₁₀ alkyl chain orR₄X(CH₂)_(n), X is —O—, —C(O)NH— or —NH—, R₄ is a C₆–C₁₂ alkyl chain nis between 1 to 5, preferably 3. R₁ alkyl chains can be straight orbranched and can be interrupted with up to 12, preferably less than 5ethylene oxide moieties.

Preferred amines according to the formula herein above are n-alkylamines. Suitable amines for use herein can be selected from1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Otherpreferred primary amines include C8–C10 oxypropylamine,octyloxypropylamine, 2-ethylhexyl-oxypropylamine, lauryl amidopropylamine and amido propylamine.

Suitable tertiary amines for use herein include tertiary amines havingthe formula R₁R₂R₃N wherein R₁ and R₂ are C₁–C₈ alkyl chains or

R₃ is either a C₆–C₁₂, preferably C₆–C₁₀ alkyl chain, or R₃ isR₄X(CH₂)_(n), whereby X is —O—, —C(O)NH— or —NH—,R₄ is a C₄–C₁₂, n isbetween 1 to 5, preferably 2–3, R₅ is H or C₁–C₂ alkyl and x is between1 to 6.

R₃ and R₄ can be linear or branched; R₃ alkyl chains can be interruptedwith up to 12, preferably less than 5, ethylene oxide moieties.

Preferred tertiary amines are R₁R₂R₃N where R₁ is a C₆–C₁₂ alkyl chain,R₂ and R₃ are C₁–C₃ alkyl or

where R₅ is H or CH₃ and x=1–2.

Also preferred are the amidoamines of the formula:

wherein R₁ is C₆–C₁₂ alkyl; n is 2–4,preferably n is 3; R₂ and R₃ is C₁–C₄

Most preferred amines of the present invention include 1-octylamine,1-hexylamine, 1-decylamine, 1-dodecylamine,C8–10oxypropylamine, N coco1–3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine,lauryl bis(hydroxyethyl)amine, coco bis(hydroxyethyl)amine, lauryl amine2 moles propoxylated, octyl amine 2 moles propoxylated, laurylamidopropyldimethylamine, C8–10 amidopropyldimethylamine and C10amidopropyldimethylamine.

The most preferred amines for use in the compositions herein are1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Especiallydesirable are n-dodecyldimethylamine andbishydroxyethylcoconutalkylamine and oleylamine 7 times ethoxylated,lauryl amido propylamine and cocoamido propylamine.

Odor Control Agent

The compositions for odor control are of the type disclosed in U.S. Pat.Nos. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2,1997; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, allof said patents being incorporated herein by reference. Fabric carecompositions of the present invention can contain several differentoptional odor control agents, preferably cyclodextrins, water solublezinc salts, water soluble copper salts, and mixtures thereof.

(a). Cyclodextrin

As used herein, the term “cyclodextrin” includes any of the knowncyclodextrins such as unsubstituted cyclodextrins containing from six totwelve glucose units, especially, alpha-cyclodextrin, beta-cyclodextrin,gamma-cyclodextrin and/or their derivatives and/or mixtures thereof. Thealpha-cyclodextrin consists of six glucose units, the beta-cyclodextrinconsists of seven glucose units, and the gamma-cyclodextrin consists ofeight glucose units arranged in donut-shaped rings. The specificcoupling and conformation of the glucose units give the cyclodextrins arigid, conical molecular structures with hollow interiors of specificvolumes. The “lining” of each internal cavity is formed by hydrogenatoms and glycosidic bridging oxygen atoms; therefore, this surface isfairly hydrophobic. The unique shape and physical-chemical properties ofthe cavity enable the cyclodextrin molecules to absorb (form inclusioncomplexes with) organic molecules or parts of organic molecules whichcan fit into the cavity. Many odorous molecules can fit into the cavityincluding many malodorous molecules and perfume molecules. Therefore,cyclodextrins, and especially mixtures of cyclodextrins with differentsize cavities, can be used to control odors caused by a broad spectrumof organic odoriferous materials, which may, or may not, containreactive functional groups. The complexation between cyclodextrin andodorous molecules occurs rapidly in the presence of water. However, theextent of the complex formation also depends on the polarity of theabsorbed molecules. In an aqueous solution, strongly hydrophilicmolecules (those which are highly water-soluble) are only partiallyabsorbed, if at all. Therefore, cyclodextrin does not complexeffectively with some very low molecular weight organic amines and acidswhen they are present at low levels on wet fabrics. As the water isbeing removed however, e.g., the fabric is being dried off, some lowmolecular weight organic amines and acids have more affinity and willcomplex with the cyclodextrins more readily.

The cavities within the cyclodextrin in the solution of the presentinvention should remain essentially unfilled (the cyclodextrin remainsuncomplexed) while in solution, in order to allow the cyclodextrin toabsorb various odor molecules when the solution is applied to a surface.Non-derivatised (normal) beta-cyclodextrin can be present at a level upto its solubility limit of about 1.85% (about 1.85 g in 100 grams ofwater) at room temperature. Beta-cyclodextrin is not preferred incompositions which call for a level of cyclodextrin higher than itswater solubility limit. Non-derivatised beta-cyclodextrin is generallynot preferred when the composition contains surfactant since it affectsthe surface activity of most of the preferred surfactants that arecompatible with the derivatised cyclodextrins.

Preferably, the odor absorbing solution of the present invention isclear. The term “clear” as defined herein means transparent ortranslucent, preferably transparent, as in “water clear,” when observedthrough a layer having a thickness of less than about 10 cm.

Preferably, the cyclodextrins used in the present invention are highlywater-soluble such as, alpha-cyclodextrin and/or derivatives thereof,gamma-cyclodextrin and/or derivatives thereof, derivatisedbeta-cyclodextrins, and/or mixtures thereof. The derivatives ofcyclodextrin consist mainly of molecules wherein some of the OH groupsare converted to OR groups. Cyclodextrin derivatives include, e.g.,those with short chain alkyl groups such as methylated cyclodextrins,and ethylated cyclodextrins, wherein R is a methyl or an ethyl group;those with hydroxyalkyl substituted groups, such as hydroxypropylcyclodextrins and/or hydroxyethyl cyclodextrins, wherein R is a—CH₂—CH(OH)—CH₃ or a —CH₂CH₂—OH group; branched cyclodextrins such asmaltose-bonded cyclodextrins; cationic cyclodextrins such as thosecontaining 2-hydroxy-3-(dimethylamino)propyl ether, wherein R isCH₂—CH(OH)—CH₂—N(CH₃)₂ which is cationic at low pH; quaternary ammonium,e.g., 2-hydroxy-3-(trimethylammonio)propyl ether chloride groups,wherein R is CH₂—CH(OH)—CH₂—N⁺(CH₃)₃Cl⁻; anionic cyclodextrins such ascarboxymethyl cyclodextrins, cyclodextrin sulfates, and cyclodextrinsuccinylates; amphoteric cyclodextrins such as carboxymethyl/quaternaryammonium cyclodextrins; cyclodextrins wherein at least one glucopyranoseunit has a 3–6-anhydro-cyclomalto structure, e.g., themono-3–6-anhydrocyclodextrins, as disclosed in “Optimal Performanceswith Minimal Chemical Modification of Cyclodextrins”, F. Diedaini-Pilardand B. Perly, The 7th International Cyclodextrin Symposium Abstracts,April 1994, p. 49, said references being incorporated herein byreference; and mixtures thereof. Other cyclodextrin derivatives aredisclosed in U.S. Pat. No. 3,426,011, Parmerter et al., issued Feb. 4,1969; U.S. Pat. Nos. 3,453,257; 3,453,258; 3,453,259; and 3,453,260, allin the names of Parmerter et al., and all issued Jul. 1, 1969; U.S. Pat.No. 3,459,731, Gramera et al., issued Aug. 5, 1969; U.S. Pat. No.3,553,191, Parmerter et al., issued Jan. 5, 1971; U.S. Pat. No.3,565,887, Parmerter et al., issued Feb. 23, 1971; U.S. Pat. No.4,535,152, Szejtli et al., issued Aug. 13, 1985; U.S. Pat. No.4,616,008, Hirai et al., issued Oct. 7, 1986; U.S. Pat. No. 4,678,598,Ogino et al., issued Jul. 7, 1987; U.S. Pat. No. 4,638,058, Brandt etal., issued Jan. 20, 1987; and U.S. Pat. No. 4,746,734, Tsuchiyama etal., issued May 24, 1988; all of said patents being incorporated hereinby reference.

Highly water-soluble cyclodextrins are those having water solubility ofat least about 10 g in 100 ml of water at room temperature, preferablyat least about 20 g in 100 ml of water, more preferably at least about25 g in 100 ml of water at room temperature. The availability ofsolubilized, uncomplexed cyclodextrins is essential for effective andefficient odor control performance. Solubilized, water-solublecyclodextrin can exhibit more efficient odor control performance thannon-water-soluble cyclodextrin when deposited onto surfaces, especiallyfabric.

Examples of preferred water-soluble cyclodextrin derivatives suitablefor use herein are hydroxypropyl alpha-cyclodextrin, methylatedalpha-cyclodextrin, methylated beta-cyclodextrin, hydroxyethylbeta-cyclodextrin, and hydroxypropyl beta-cyclodextrin. Hydroxyalkylcyclodextrin derivatives preferably have a degree of substitution offrom about 1 to about 14, more preferably from about 1.5 to about 7,wherein the total number of OR groups per cyclodextrin is defined as thedegree of substitution. Methylated cyclodextrin derivatives typicallyhave a degree of substitution of from about 1 to about 18, preferablyfrom about 3 to about 16. A known methylated beta-cyclodextrin isheptakis-2,6-di-O-methyl-β-cyclodextrin, commonly known as DIMEB, inwhich each glucose unit has about 2 methyl groups with a degree ofsubstitution of about 14. A preferred, more commercially available,methylated beta-cyclodextrin is a randomly methylated beta-cyclodextrin,commonly known as RAMEB, having different degrees of substitution,normally of about 12.6. RAMEB is more preferred than DIMEB, since DIMEBaffects the surface activity of the preferred surfactants more thanRAMEB. The preferred cyclodextrins are available, e.g., from CerestarUSA, Inc. and Wacker Chemicals (USA), Inc.

It is also preferable to use a mixture of cyclodextrins. Such mixturesabsorb odors more broadly by complexing with a wider range ofodoriferous molecules having a wider range of molecular sizes.Preferably at least a portion of the cyclodextrins is alpha-cyclodextrinand its derivatives thereof, gamma-cyclodextrin and its derivativesthereof, and/or derivatised beta-cyclodextrin, more preferably a mixtureof alpha-cyclodextrin, or an alpha-cyclodextrin derivative, andderivatised beta-cyclodextrin, even more preferably a mixture ofderivatised alpha-cyclodextrin and derivatised beta-cyclodextrin, mostpreferably a mixture of hydroxypropyl alpha-cyclodextrin andhydroxypropyl beta-cyclodextrin, and/or a mixture of methylatedalpha-cyclodextrin and methylated beta-cyclodextrin.

For controlling odor on fabrics, the composition is preferably used as aspray. Typical levels of cyclodextrin in usage compositions for usageconditions are from about 0.01% to about 5%, preferably from about 0.1%to about 4%, more preferably from about 0.5% to about 2% by weight ofthe composition. It is preferable that the treated fabric contains alevel of less than about 5 mg of cyclodextrin per gram of fabric, morepreferably less than about 2 mg of cyclodextrin per gram of fabric.

Low Molecular Weight Polyols

Low molecular weight polyols with relatively high boiling points, ascompared to water, such as ethylene glycol, propylene glycol and/orglycerol are preferred optional ingredients for improving odor controlperformance of the composition of the present invention whencyclodextrin is present. Not to be bound by theory, it is believed thatthe incorporation of a small amount of low molecular weight glycols intothe composition of the present invention enhances the formation of thecyclodextrin inclusion complexes as the fabric dries.

It is believed that the polyols' ability to remain on the fabric for alonger period of time than water, as the fabric dries allows it to formternary complexes with the cyclodextrin and some malodorous molecules.The addition of the glycols is believed to fill up void space in thecyclodextrin cavity that is unable to be filled by some malodormolecules of relatively smaller sizes. Preferably the glycol used isglycerin, ethylene glycol, propylene glycol, diethylene glycol,dipropylene glycol or mixtures thereof, more preferably ethylene glycoland/or propylene glycol. Cyclodextrins prepared by processes that resultin a level of such polyols are highly desirable, since they can be usedwithout removal of the polyols.

Some polyols, e.g., dipropylene glycol, are also useful to facilitatethe solubilization of some perfume ingredients in the composition of thepresent invention.

Typically, glycol is added to the composition of the present inventionat a level of from about 0.01% to about 3%, by weight of thecomposition, preferably from about 0.05% to about 1%, more preferablyfrom about 0.1% to about 0.5%, by weight of the composition. Thepreferred weight ratio of low molecular weight polyol to cyclodextrin isfrom about 2:1,000 to about 20:100, more preferably from about 3:1,000to about 15:100, even more preferably from about 5:1,000 to about10:100, and most preferably from about 1:100 to about 7:100.

(b). Metal Salts

Optionally, but highly preferred, the present invention can includemetallic salts for added odor absorption and/or antimicrobial benefitfor the cyclodextrin solution when cyclodextrin is present. The metallicsalts are selected from the group consisting of copper salts, zincsalts, and mixtures thereof.

Copper salts have some antimicrobial benefits. Specifically, cupricabietate acts as a fungicide, copper acetate acts as a mildew inhibitor,cupric chloride acts as a fungicide, copper lactate acts as a fungicide,and copper sulfate acts as a germicide. Copper salts also possess somemalodor control abilities. See U.S. Pat. No. 3,172,817, Leupold, et al.,which discloses deodorizing compositions for treating disposablearticles, comprising at least slightly water-soluble salts ofacylacetone, including copper salts and zinc salts, all of said patentsare incorporated herein by reference.

The preferred zinc salts possess malodor control abilities. Zinc hasbeen used most often for its ability to ameliorate malodor, e.g., inmouth wash products, as disclosed in U.S. Pat. No. 4,325,939, issuedApr. 20, 1982 and U.S. Pat. No. 4,469,674, issued Sep. 4, 1983, to N. B.Shah, et al., all of which are incorporated herein by reference.Highly-ionized and soluble zinc salts such as zinc chloride, provide thebest source of zinc ions. Zinc borate functions as a fungistat and amildew inhibitor, zinc caprylate functions as a fungicide, zinc chlorideprovides antiseptic and deodorant benefits, zinc ricinoleate functionsas a fungicide, zinc sulfate heptahydrate functions as a fungicide andzinc undecylenate functions as a fungistat.

Preferably the metallic salts are water-soluble zinc salts, copper saltsor mixtures thereof, and more preferably zinc salts, especially ZnCl₂.These salts are preferably present in the present invention primarily toabsorb amine and sulfur-containing compounds that have molecular sizestoo small to be effectively complexed with the cyclodextrin molecules.Low molecular weight sulfur-containing materials, e.g., sulfide andmercaptans, are components of many types of malodors, e.g., food odors(garlic, onion), body/perspiration odor, breath odor, etc. Low molecularweight amines are also components of many malodors, e.g., food odors,body odors, urine, etc.

When metallic salts are added to the composition of the presentinvention they are typically present at a level of from about 0.1% toabout 10%, preferably from about 0.2% to about 8%, more preferably fromabout 0.3% to about 5% by weight of the usage composition. When zincsalts are used as the metallic salt, and a clear solution is desired, itis preferable that the pH of the solution is adjusted to less than about7, more preferably less than about 6, most preferably, less than about5, in order to keep the solution clear.

(c). Soluble Carbonate and/or Bicarbonate Salts

Water-soluble alkali metal carbonate and/or bicarbonate salts, such assodium bicarbonate, potassium bicarbonate, potassium carbonate, cesiumcarbonate, sodium carbonate, and mixtures thereof can be added to thecomposition of the present invention in order to help to control certainacid-type odors. Preferred salts are sodium carbonate monohydrate,potassium carbonate, sodium bicarbonate, potassium bicarbonate, andmixtures thereof. When these salts are added to the composition of thepresent invention, they are typically present at a level of from about0.1% to about 5%, preferably from about 0.2% to about 3%, morepreferably from about 0.3% to about 2%, by weight of the composition.When these salts are added to the composition of the present inventionit is preferably that incompatible metal salts not be present in theinvention. Preferably, when these salts are used the composition shouldbe essentially free of zinc and other incompatible metal ions, e.g., Ca,Fe, Ba, etc. which form water-insoluble salts.

(d). Zeolites

When the clarity of the solution is not needed, and the solution is notsprayed on fabrics, other optional odor absorbing materials, e.g.,zeolites and/or activated carbon, can also be used. A preferred class ofzeolites is characterized as “intermediate” silicate/aluminate zeolites.The intermediate zeolites are characterized by SiO₂/AlO₂ molar ratios ofless than about 10. Preferably the molar ratio of SiO₂/AlO₂ ranges fromabout 2 to about 10. The intermediate zeolites have an advantage overthe “high” zeolites. The intermediate zeolites have a higher affinityfor amine-type odors, they are more weight efficient for odor absorptionbecause they have a larger surface area, and they are more moisturetolerant and retain more of their odor absorbing capacity in water thanthe high zeolites. A wide variety of intermediate zeolites suitable foruse herein are commercially available as Valfor® CP301-68, Valfor®300-63, Valfor® CP300-35, and Valfor® CP300-56, available from PQCorporation, and the CBV100® series of zeolites from Conteka.

Zeolite materials marketed under the trade name Abscents® andSmellrite®, available from The Union Carbide Corporation and UOP arealso preferred. These materials are typically available as a whitepowder in the 3–5 micron particle size range. Such materials arepreferred over the intermediate zeolites for control ofsulfur-containing odors, e.g., thiols, mercaptans.

-   -   (e). Activated Carbon

The carbon material suitable for use in the present invention is thematerial well known in commercial practice as an absorbent for organicmolecules and/or for air purification purposes. Often, such carbonmaterial is referred to as “activated” carbon or “activated” charcoal.Such carbon is available from commercial sources under such trade namesas; Calgon-Type CPG®; Type PCB®; Type SGL®; Type CAL®; and Type OL®.

(f). Mixtures Thereof

Mixtures of the above materials are desirable, especially when themixture provides control over a broader range of odors.

Perfume

The fabric care composition of the present invention can also optionallyprovide a “scent signal” in the form of a pleasant odor which provides afreshness impression to the treated fabrics. The scent signal can bedesigned to provide a fleeting perfume scent. When perfume is added as ascent signal, it is added only at very low levels, e.g., from about0.001% to about 0.5%, preferably from about 0.003% to about 0.3%, morepreferably from about 0.005% to about 0.2%, by weight of the usagecomposition.

Perfume can also be added as a more intense odor in product and onfabrics. When stronger levels of perfume are preferred, relativelyhigher levels of perfume can be added.

Any type of perfume can be incorporated into the composition of thepresent invention. The preferred perfume ingredients are those suitablefor use to apply on fabrics and garments. Typical examples of suchpreferred ingredients are given in U.S. Pat. No. 5,445,747, issued Aug.29, 1995 to Kvietok et al., incorporated herein by reference.

When long lasting fragrance odor on fabrics is desired, it is preferredto use at least an effective amount of substantive perfume ingredients.Nonlimiting examples of such preferred ingredients are given in U.S.Pat. Nos. 5,500,138 and 5,652,206, issued Mar. 19, 1996 and Jul. 29,1997, respectively, to Bacon et al., said patents being incorporatedherein by reference. It is also preferred to use materials that canslowly release perfume ingredients after the fabric is treated by thefabric care composition of this invention. Examples of materials of thistype are given in U.S. Pat. No. 5,531,910, Severns et al., issued Jul.2, 1996, said patent being incorporated herein by reference.

As used herein, perfume includes fragrant substance or mixture ofsubstances including natural (i.e., obtained by extraction of flowers,herbs, leaves, roots, barks, wood, blossoms or plants), artificial(i.e., a mixture of different nature oils or oil constituents) andsynthetic (i.e., synthetically produced) odoriferous substances. Suchmaterials are often accompanied by auxiliary materials, such asfixatives, extenders, stabilizers and solvents. These auxiliaries arealso included within the meaning of “perfume”, as used herein.Typically, perfumes are complex mixtures of a plurality of organiccompounds.

Examples of perfume ingredients useful in the perfumes of the presentinvention compositions include, but are not limited to, those materialsdisclosed in said patents.

The perfumes useful in the present invention compositions are preferablysubstantially free of halogenated materials and nitromusks.

Suitable solvents, diluents or carriers for perfumes ingredientsmentioned above are for examples, ethanol, isopropanol, diethyleneglycol, monoethyl ether, dipropylene glycol, diethyl phthalate, triethylcitrate, etc. The amount of such solvents, diluents or carriersincorporated in the perfumes is preferably kept to the minimum needed toprovide a homogeneous perfume solution.

Perfume can be present at a level of from 0% to about 15%, preferablyfrom about 0.1% to about 8%, and more preferably from about 0.2% toabout 5%, by weight of the finished fabric care composition.

When cyclodextrin is present, it is essential that the perfume be addedat a level wherein even if all of the perfume in the composition were tocomplex with the cyclodextrin molecules when cyclodextrin is present,there will still be an effective level of uncomplexed cyclodextrinmolecules present in the solution to provide adequate odor control. Inorder to reserve an effective amount of cyclodextrin molecules for odorcontrol when cyclodextrin is present, perfume is typically present at alevel wherein less than about 90% of the cyclodextrin complexes with theperfume, preferably less than about 50% of the cyclodextrin complexeswith the perfume, more preferably, less than about 30% of thecyclodextrin complexes with the perfume, and most preferably, less thanabout 10% of the cyclodextrin complexes with the perfume. Thecyclodextrin to perfume weight ratio should be greater than about 8:1,preferably greater than about 10:1, more preferably greater than about20:1, even more preferably greater than 40:1 and most preferably greaterthan about 70:1.

Preferably the perfume is hydrophilic and is composed predominantly ofingredients selected from two groups of ingredients, namely, (a)hydrophilic ingredients having a ClogP of less than about 3.5, morepreferably less than about 3.0, and (b) ingredients having significantlow detection threshold, and mixtures thereof. Typically, at least about50%, preferably at least about 60%, more preferably at least about 70%,and most preferably at least about 80% by weight of the perfume iscomposed of perfume ingredients of the above groups (a) and (b). Forthese preferred perfumes, the cyclodextrin to perfume weight ratio istypically of from about 2:1 to about 200:1; preferably from about 4:1 toabout 100:1, more preferably from about 6:1 to about 50:1, and even morepreferably from about 8:1 to about 30:1.

(a). Hydrophilic Perfume Ingredients

The hydrophilic perfume ingredients are more soluble in water, have lessof a tendency to complex with the cyclodextrins, and are more availablein the odor absorbing composition than the ingredients of conventionalperfumes. The degree of hydrophobicity of a perfume ingredient can becorrelated with its octanol/water partition coefficient P. Theoctanol/water partition coefficient of a perfume ingredient is the ratiobetween its equilibrium concentration in octanol and in water. A perfumeingredient with a greater partition coefficient P is considered to bemore hydrophobic. Conversely, a perfume ingredient with a smallerpartition coefficient P is considered to be more hydrophilic. Since thepartition coefficients of the perfume ingredients normally have highvalues, they are more conveniently given in the form of their logarithmto the base 10, logP. Thus the preferred perfume hydrophilic perfumeingredients of this invention have logP of about 3.5 or smaller,preferably of about 3.0 or smaller.

The logP of many perfume ingredients have been reported; for example,the Pomona92 database, available from Daylight Chemical InformationSystems, Inc. (Daylight CIS), Irvine, Calif., contains many, along withcitations to the original literature. However, the logP values are mostconveniently calculated by the “CLOGP” program, also available fromDaylight CIS. This program also lists experimental logP values when theyare available in the Pomona92 database. The “calculated logP” (ClogP) isdetermined by the fragment approach of Hansch and Leo (cf., A. Leo, inComprehensive Medicinal Chemistry, Vol. 4, C. Hansch, P. G. Sammens, J.B. Taylor and C. A. Ramsden, Eds., p. 295, Pergamon Press, 1990,incorporated herein by reference). The fragment approach is based on thechemical structure of each perfume ingredient, and takes into accountthe numbers and types of atoms, the atom connectivity, and chemicalbonding. The ClogP values, which are the most reliable and widely usedestimates for this physicochemical property, are used instead of theexperimental logP values in the selection of perfume ingredients whichare useful in the present invention.

Non-limiting examples of the more preferred hydrophilic perfumeingredients are allyl amyl glycolate, allyl caproate, amyl acetate, amylpropionate, anisic aldehyde, anisyl acetate, anisole, benzaldehyde,benzyl acetate, benzyl acetone, benzyl alcohol, benzyl formate, benzyliso valerate, benzyl propionate, beta gamma hexenol, calone, camphorgum, laevo-carveol, d-carvone, laevo-carvone, cinnamic alcohol, cinnamylacetate, cinnamic alcohol, cinnamyl formate, cinnamyl propionate,cis-jasmone, cis-3-hexenyl acetate, coumarin, cuminic alcohol, cuminicaldehyde, Cyclal C, cyclogalbanate, dihydroeuginol, dihydroisojasmonate, dimethyl benzyl carbinol, dimethyl benzyl carbinylacetate, ethyl acetate, ethyl aceto acetate, ethyl amyl ketone, ethylanthranilate, ethyl benzoate, ethyl butyrate, ethyl cinnamate, ethylhexyl ketone, ethyl maltol, ethyl-2-methyl butyrate, ethyl methylphenylglycidate, ethyl phenyl acetate, ethyl salicylate, ethyl vanillin,eucalyptol, eugenol, eugenyl acetate, eugenyl formate, eugenyl methylether, fenchyl alcohol, flor acetate (tricyclo decenyl acetate),fructone, frutene (tricyclo decenyl propionate), geraniol, geranyloxyacetaldehyde, heliotropin, hexenol, hexenyl acetate, hexyl acetate,hexyl formate, hinokitiol, hydrotropic alcohol, hydroxycitronellal,hydroxycitronellal diethyl acetal, hydroxycitronellol, indole, isoamylalcohol, iso cyclo citral, isoeugenol, isoeugenyl acetate, isomenthone,isopulegyl acetate, isoquinoline, keone, ligustral, linalool, linalooloxide, linalyl formate, lyral, menthone, methyl acetophenone, methylamyl ketone, methyl anthranilate, methyl benzoate, methyl benzylacetate, methyl cinnamate, methyl dihydrojasmonate, methyl eugenol,methyl heptenone, methyl heptine carbonate, methyl heptyl ketone, methylhexyl ketone, methyl isobutenyl tetrahydropyran, methyl-N-methylanthranilate, methyl beta naphthyl ketone, methyl phenyl carbinylacetate, methyl salicylate, nerol, nonalactone, octalactone, octylalcohol (octanol-2), para-anisic aldehyde, para-cresol, para-cresylmethyl ether, para hydroxy phenyl butanone, para-methoxy acetophenone,para-methyl acetophenone, phenoxy ethanol, phenoxyethyl propionate,phenyl acetaldehyde, phenylacetaldehyde diethyl ether, phenylethyloxyacetaldehyde, phenyl ethyl acetate, phenyl ethyl alcohol, phenylethyl dimethyl carbinol, prenyl acetate, propyl butyrate, pulegone, roseoxide, safrole, terpineol, vanillin, viridine, and mixtures thereof.

Nonlimiting examples of other preferred hydrophilic perfume ingredientswhich can be used in perfume compositions of this invention are allylheptoate, amyl benzoate, anethole, benzophenone, carvacrol, citral,citronellol, citronellyl nitrile, cyclohexyl ethyl acetate, cymal,4-decenal, dihydro isojasmonate, dihydro myrcenol, ethyl methyl phenylglycidate, fenchyl acetate, florhydral, gamma-nonalactone, geranylformate, geranyl nitrile, hexenyl isobutyrate, alpha-ionone, isobornylacetate, isobutyl benzoate, isononyl alcohol, isomenthol, para-isopropylphenylacetaldehyde, isopulegol, linalyl acetate, 2-methoxy naphthalene,menthyl acetate, methyl chavicol, musk ketone, beta naphthol methylether, neral, nonyl aldehyde, phenyl heptanol, phenyl hexanol, terpinylacetate, Veratrol, yara—yara, and mixtures thereof.

The preferred perfume compositions used in the present invention containat least 4 different hydrophilic perfume ingredients, preferably atleast 5 different hydrophilic perfume ingredients, more preferably atleast 6 different hydrophilic perfume ingredients, and even morepreferably at least 7 different hydrophilic perfume ingredients. Mostcommon perfume ingredients which are derived from natural sources arecomposed of a multitude of components. When each such material is usedin the formulation of the preferred perfume compositions of the presentinvention, it is counted as one single ingredient, for the purpose ofdefining the invention.

(b). Low Odor Detection Threshold Perfume Ingredients

The odor detection threshold of an odorous material is the lowest vaporconcentration of that material which can be olfactorily detected. Theodor detection threshold and some odor detection threshold values arediscussed in, e.g., “Standardized Human Olfactory Thresholds”, M. Devoset al, IRL Press at Oxford University Press, 1990, and “Compilation ofOdor and Taste Threshold Values Data”, F. A. Fazzalari, editor, ASTMData Series DS 48A, American Society for Testing and Materials, 1978,both of said publications being incorporated by reference. The use ofsmall amounts of perfume ingredients that have low odor detectionthreshold values can improve perfume odor character, even though theyare not as hydrophilic as perfume ingredients of group (a) which aregiven hereinabove. Perfume ingredients that do not belong to group (a)above, but have a significantly low detection threshold, useful in thecomposition of the present invention, are selected from the groupconsisting of ambrox, bacdanol, benzyl salicylate, butyl anthranilate,cetalox, damascenone, alpha-damascone, gamma-dodecalactone, ebanol,herbavert, cis-3-hexenyl salicylate, alpha-ionone, beta-ionone,alpha-isomethylionone, lilial, methyl nonyl ketone, gamma-undecalactone,undecylenic aldehyde, and mixtures thereof. These materials arepreferably present at low levels in addition to the hydrophilicingredients of group (a), typically less than about 20%, preferably lessthan about 15%, more preferably less than about 10%, by weight of thetotal perfume compositions of the present invention. However, only lowlevels are required to provide an effect.

There are also hydrophilic ingredients of group (a) that have asignificantly low detection threshold, and are especially useful in thecomposition of the present invention. Examples of these ingredients areallyl amyl glycolate, anethole, benzyl acetone, calone, cinnamicalcohol, coumarin, cyclogalbanate, Cyclal C, cymal, 4-decenal, dihydroisojasmonate, ethyl anthranilate, ethyl-2-methyl butyrate, ethylmethylphenyl glycidate, ethyl vanillin, eugenol, flor acetate,florhydral, fructone, frutene, heliotropin, keone, indole, iso cyclocitral, isoeugenol, lyral, methyl heptine carbonate, linalool, methylanthranilate, methyl dihydrojasmonate, methyl isobutenyltetrahydropyran, methyl beta naphthyl ketone, beta naphthol methylether, nerol, para-anisic aldehyde, para hydroxy phenyl butanone, phenylacetaldehyde, vanillin, and mixtures thereof. Use of low odor detectionthreshold perfume ingredients minimizes the level of organic materialthat is released into the atmosphere.

Antimicrobial Active

Optionally, the fabric care composition of the present inventioncomprise an effective amount, to kill, or reduce the growth of microbes,of antimicrobial active; preferably from about 0.001% to about 2%, morepreferably from about 0.002% to about 1%, even more preferably fromabout 0.003% to about 0.3%, by weight of the usage composition. Theeffective antimicrobial active can function as disinfectants/sanitizers,and is useful in providing protection against organisms that becomeattached to the fabrics.

Given below are nonlimiting examples of antimicrobial actives which areuseful in the present invention:

-   Pyrithiones, especially the zinc complex (ZPT); Octopirox; Parabens,    including Methylparaben, Propylparaben, Butylparaben, Ethylparaben,    Isopropylparaben, Isobutylparaben, Benzylparaben, Sodium    Methylparaben, and Sodium Propylparaben; DMDM Hydantoin (Glydant);    Methylchloroisothiazolinone/methylisothiazolinone (Kathon CG);    Sodium Sulfite; Sodium Bisulfite; Imidazolidinyl Urea; Diazolidinyl    Urea (Germail 2); Sorbic Acid/Potassium Sorbate; Dehydroacetic    Acid/Sodium Dehydroacetate; Benzyl Alcohol; Sodium Borate;    2-Bromo-2-nitropropane-1,3-diol (Bronopol); Formalin; Iodopropynyl    Butylcarbamate; Boric Acid; Chloroacetamide; Methenamine;    Methyldibromo Glutaronitrile; Glutaraldehyde; Hexamidine    Isethionate; 5-bromo-5-nitro-1,3-dioxane; Phenethyl Alcohol;    o-Phenylphenol/sodium o-phenylphenol; Sodium Hydroxymethylglycinate;    Polymethoxy Bicyclic Oxazolidine; Dimethoxane; Thimersol;    Dichlorobenzyl alcohol; Captan; Chlorphenenesin; Dichlorophene;    Chlorbutanol; Phenoxyethanol; Phenoxyisopropanol; Halogenated    Diphenyl Ethers; 2,4,4′-trichloro-2′-hydroxy-diphenyl ether    (Triclosan); 2,2′-dihydroxy-5,5′-dibromo-diphenyl ether;-   Phenolic Compounds—(including phenol and its homologs, mono- and    poly-alkyl and aromatic halophenols, resorcinol and its derivatives,    bisphenolic compounds and halogenated salicylanilides); Phenol and    its Homologs including Phenol, 2-Methyl Phenol, 3-Methyl Phenol,    4-Methyl Phenol, 4-Ethyl Phenol, 2,4-Dimethyl Phenol, 2,5-Dimethyl    Phenol, 3,4-Dimethyl Phenol, 2,6-Dimethyl Phenol, 4-n-Propyl Phenol,    4-n-Butyl Phenol, 4-n-Amyl Phenol, 4-tert-Amyl Phenol, 4-n-Hexyl    Phenol, and 4-n-Heptyl Phenol; Mono- and Poly-Alkyl and Aromatic    Halophenols including p-Chlorophenol, Methyl p-Chlorophenol, Ethyl    p-Chlorophenol, n-Propyl p-Chlorophenol, n-Butyl p-Chlorophenol,    n-Amyl p-Chlorophenol, sec-Amyl p-Chlorophenol, n-Hexyl    p-Chlorophenol, Cyclohexyl p-Chlorophenol, n-Heptyl p-Chlorophenol,    n-Octyl p-Chlorophenol, o-Chlorophenol, Methyl o-Chlorophenol, Ethyl    o-Chlorophenol, n-Propyl o-Chlorophenol, n-Butyl o-Chlorophenol,    n-Amyl o-Chlorophenol, tert-Amyl o-Chlorophenol, n-Hexyl    o-Chlorophenol, n-Heptyl o-Chlorophenol, o-Benzyl p-Chlorophenol,    o-benzyl-m-methyl p-Chlorophenol, o-Benzyl-m, m-dimethyl    p-Chlorophenol, o-Phenylethyl p-Chlorophenol, o-Phenylethyl-m-methyl    p-Chlorophenol, 3-Methyl p-Chlorophenol, 3,5-Dimethyl    p-Chlorophenol, 6-Ethyl-3-methyl p-Chlorophenol, 6-n-Propyl-3-methyl    p-Chlorophenol, 6-iso-Propyl-3-methyl p-Chlorophenol,    2-Ethyl-3,5-dimethyl p-Chlorophenol, 6-sec-Butyl-3-methyl    p-Chlorophenol, 2-iso-Propyl-3,5-dimethyl p-Chlorophenol,    6-Diethylmethyl-3-methyl p-Chlorophenol,    6-iso-Propyl-2-ethyl-3-methyl p-Chlorophenol,    2-sec-Amyl-3,5-dimethyl p-Chlorophenol, 2-Diethylmethyl-3,5-dimethyl    p-Chlorophenol, 6-sec-Octyl-3-methyl p-Chlorophenol,    p-Chloro-m-cresol, p-Bromophenol, Methyl p-Bromophenol, Ethyl    p-Bromophenol, n-Propyl p-Bromophenol, n-Butyl p-Bromophenol, n-Amyl    p-Bromophenol, sec-Amyl p-Bromophenol, n-Hexyl p-Bromophenol,    cyclohexyl p-Bromophenol, o-Bromophenol, tert-Amyl o-Bromophenol,    n-Hexyl o-Bromophenol, n-Propyl-m,m-Dimethyl o-Bromophenol, 2-Phenyl    Phenol, 4-Chloro-2-methyl phenol,    -   4-Chloro-3-methyl phenol, 4-Chloro-3,5-dimethyl phenol,        2,4-dichloro-3,5-dimethylphenol,        3,4,5,6-terabromo-2-methylphenol, 5-methyl-2-pentylphenol,        4-isopropyl-3-methylphenol, para-chloro-meta-xylenol (PCMX),        5-Chloro-2-hydroxydiphenylmethane; Resorcinol and its        Derivatives including Resorcinol, Methyl Resorcinol, Ethyl        Resorcinol, n-Propyl Resorcinol, n-Butyl Resorcinol, n-Amyl        Resorcinol, n-Hexyl Resorcinol, n-Heptyl Resorcinol, n-Octyl        Resorcinol, n-Nonyl Resorcinol, Phenyl Resorcinol, Benzyl        Resorcinol, Phenylethyl Resorcinol, Phenylpropyl Resorcinol,        p-Chlorobenzyl Resorcinol, 5-Chloro 2,4-Dihydroxydiphenyl        Methane, 4′-Chloro 2,4-Dihydroxydiphenyl Methane, 5-Bromo        2,4-Dihydroxydiphenyl Methane, and 4′-Bromo        2,4-Dihydroxydiphenyl Methane; Bisphenolic Compounds including        2,2′-, methylene bis (4-chlorophenol), 2,2′-methylene bis        (3,4,6-trichlorophenol), 2,2′-methylene bis        (4-chloro-6-bromophenol), bis (2-hydroxy-3,5-dichlorophenyl)        sulphide, and bis (2-hydroxy-5-chlorobenzyl)sulphide; Benzoic        Esters including p-Hydroxybenzoic Acid, Methyl p-Hydroxybenzoic        Acid, Ethyl p-Hydroxybenzoic Acid, Propyl p-Hydroxybenzoic Acid,        and Butyl p-Hydroxybenzoic Acid.

Another class of antibacterial agents, which are useful in the presentinvention, are the so-called “natural” antibacterial actives, referredto as natural essential oils. These actives derive their names fromtheir natural occurrence in plants. Typical natural essential oilantibacterial actives include oils of anise, lemon, orange, rosemary,wintergreen, thyme, lavender, cloves, hops, tea tree, citronella, wheat,barley, lemongrass, cedar leaf, cedarwood, cinnamon, fleagrass,geranium, sandalwood, violet, cranberry, eucalyptus, vervain,peppermint, gum benzoin, Hydastis carradensis, Berberidaceae. daceae,Ratanhiae and Curcuma longa. Also included in this class of naturalessential oils are the key chemical components of the plant oils whichhave been found to provide the antimicrobial benefit. These chemicalsinclude, but are not limited to anethol, catechole, camphene, thymol,eugenol, eucalyptol, ferulic acid, farnesol, hinokitiol, tropolone,limonene, menthol, methyl salicylate, salicylic acid, thymol, terpineol,verbenone, berberine, ratanhiae extract, caryophellene oxide,citronellic acid, curcumin, nerolidol, geraniol and benzoic acid.

Additional active agents are antibacterial metal salts. This classgenerally includes salts of metals in groups 3b–7b, 8 and 3a–5a.Specifically are the salts of aluminum, zirconium, zinc, silver, gold,copper, lanthanum, tin, mercury, bismuth, selenium, strontium, scandium,yttrium, cerium, praseodymiun, neodymium, promethum, samarium, europium,gadolinium, terbium, dysprosium, holmium, erbium, thulium, ytterbium,lutetium and mixtures thereof.

Preferred antimicrobial agents for use herein are the broad spectrumactives selected from the group consisting of Triclosan,phenoxyisopropanol, phenoxyethanol, PCMX, natural essential oils andtheir key ingredients, and mixtures thereof. The most preferredantimicrobial active for use in the present invention is Triclosan.

Quaternary Compounds. A wide range of quaternary compounds can also beused as antimicrobial actives, in conjunction with the preferredsurfactants, for compositions of the present invention. Non-limitingexamples of useful quaternary compounds include: (1) benzalkoniumchlorides and/or substituted benzalkonium chlorides such as commerciallyavailable Barquat® (available from Lonza), Maquat® (available fromMason), Variquat® (available from Witco/Sherex), and Hyamine® (availablefrom Lonza); (2) di(C6–C 14)alkyl di-short chain (C₁₋₄ alkyl and/orhydroxyalkyl) quaternary such as Bardac® products of Lonza. Thesequaternary compounds contain two relatively short chains, e.g., C₁₋₄alkyl and/or hydroxy alkyl groups and two C₆₋₁₂, preferably C₆₋₁₀, andmore preferably C₈, alkyl groups, (3) N-(3-chloroallyl) hexaminiumchlorides such as Dowicide® and Dowicil® available from Dow; (4)benzethonium chloride such as Hyamine® 1622 from Rohm & Haas; (5)methylbenzethonium chloride represented by Hyamine® 10X supplied by Rohm& Haas, (6) cetylpyridinium chloride such as Cepacol chloride availablefrom of Merrell Labs. Examples of the preferred dialkyl quaternarycompounds are di(C₈–C₁₂)dialkyl dimethyl ammonium chloride, such asdidecyldimethylammonium chloride (Bardac 22), anddioctyldimethylammonium chloride (Bardac 2050). Typical concentrationsfor biocidal effectiveness of these quaternary compounds range fromabout 0.001% to about 0.8%, preferably from about 0.005% to about 0.3%,more preferably from about 0.01% to 0.2%, by weight of the usagecomposition. The corresponding concentrations for the concentratedcompositions are from about 0.003% to about 2%, preferably from about0.006% to about 1.2%, and more preferably from about 0.1% to about 0.8%by weight of the concentrated compositions.

When cyclodextrin is present, the solubilized, water-solubleantimicrobial active is useful in providing protection against organismsthat become attached to the treated fabrics. The antimicrobial should becyclodextrin-compatible, e.g., not substantially forming complexes withthe cyclodextrin in the odor absorbing composition when cyclodextrin ispresent. The free, uncomplexed antimicrobial, e.g., antibacterial,active provides an optimum antibacterial performance.

Sanitization of fabrics can be achieved by the compositions of thepresent invention containing, antimicrobial materials, e.g.,antibacterial halogenated compounds, quaternary compounds, and phenoliccompounds.

Biguanides. Some of the more robust cyclodextrin-compatibleantimicrobial halogenated compounds which can function asdisinfectants/sanitizers as well as finish product preservatives (videinfra), and are useful in the compositions of the present inventioninclude 1,1′-hexamethylene bis(5-(p-chlorophenyl)biguanide), commonlyknown as chlorhexidine, and its salts, e.g., with hydrochloric, aceticand gluconic acids. The digluconate salt is highly water-soluble, about70% in water, and the diacetate salt has a solubility of about 1.8% inwater. When chlorhexidine is used as a sanitizer in the presentinvention it is typically present at a level of from about 0.001% toabout 0.4%, preferably from about 0.002% to about 0.3%, and morepreferably from about 0.05% to about 0.2%, by weight of the usagecomposition. In some cases, a level of from about 1% to about 2% may beneeded for virucidal activity.

Other useful biguanide compounds include Cosmoci® CQ®, Vantocil® IB,including poly (hexamethylene biguanide) hydrochloride. Other usefulcationic antimicrobial agents include the bis-biguanide alkanes. Usablewater soluble salts of the above are chlorides, bromides, sulfates,alkyl sulfonates such as methyl sulfonate and ethyl sulfonate,phenylsulfonates such as p-methylphenyl sulfonates, nitrates, acetates,gluconates, and the like.

Examples of suitable bis biguanide compounds are chlorhexidine;1,6-bis-(2-ethylhexylbiguanidohexane)dihydrochloride;1,6-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)hexane tetrahydrochloride;1,6-di-(N₁,N₁′-phenyl-N₁,N₁′-methyldiguanido-N₅,N₅′)hexanedihydrochloride; 1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexanedihydrochloride; 1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexanedihydrochloride; 1,6-di[N₁,N₁′-.beta.-(p-methoxyphenyl)diguanido-N₅,N₅′]-hexane dihydrochloride;1,6-di(N₁,N₁′-.alpha.-methyl-.beta.-phenyldiguanido-N₅,N₅′)-hexanedihydrochloride; 1,6-di(N₁,N₁′-p-nitrophenyldiguanido-N₅,N₅′)hexanedihydrochloride;.omega.:.omega.′-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)-di-n-propyletherdihydrochloride;.omega:omega′-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-di-n-propylethertetrahydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di(N₁,N₁′-p-methylphenyldiguanido-N₅,N₅′)hexanedihydrochloride;1,6-di(N₁,N₁′-2,4,5-trichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di[N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′] hexane dihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylene dihydrochloride;1,12-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′) dodecane dihydrochloride;1,10-di(N₁,N₁′-phenyldiguanido-N₅,N₅′)-decane tetrahydrochloride;1,12-di(N₁,N₁′-phenyldiguanido-N₅,N₅′) dodecane tetrahydrochloride;1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′) hexane dihydrochloride;1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;ethylene bis (1-tolyl biguanide); ethylene bis (p-tolyl biguanide);ethylene bis(3,5-dimethylphenyl biguanide); ethylenebis(p-tert-amylphenyl biguanide); ethylene bis(nonylphenyl biguanide);ethylene bis (phenyl biguanide); ethylene bis (N-butylphenyl biguanide);ethylene bis (2,5-diethoxyphenyl biguanide); ethylenebis(2,4-dimethylphenyl biguanide); ethylene bis(o-diphenylbiguanide);ethylene bis(mixed amyl naphthyl biguanide); N-butyl ethylenebis(phenylbiguanide); trimethylene bis(o-tolyl biguanide); N-butyltrimethylene bis(phenyl biguanide); and the correspondingpharmaceutically acceptable salts of all of the above such as theacetates; gluconates; hydrochlorides; hydrobromides; citrates;bisulfites; fluorides; polymaleates; N-coconutalkylsarcosinates;phosphites; hypophosphites; perfluorooctanoates; silicates; sorbates;salicylates; maleates; tartrates; fumarates;ethylenediaminetetraacetates; iminodiacetates; cinnamates; thiocyanates;arginates; pyromellitates; tetracarboxybutyrates; benzoates; glutarates;monofluorophosphates; and perfluoropropionates, and mixtures thereof.Preferred antimicrobials from this group are1,6-di-(N₁,N₁′-phenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexane dihydrochloride;1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di [N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′] hexane dihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylene dihydrochloride;1,12-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′) dodecane dihydrochloride;1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′) hexane dihydrochloride;1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;and mixtures thereof; more preferably,1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)-hexane dihydrochloride;1,6-di(N₁,N₁′-2,6-dichlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride;1,6-di(N₁,N₁′-2,4-dichlorophenyldiguanido-N₅,N₅′)hexanetetrahydrochloride; 1,6-di[N₁,N₁′-.alpha.-(p-chlorophenyl)ethyldiguanido-N₅,N₅′] hexanedihydrochloride;.omega.:.omega.′di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)m-xylenedihydrochloride; 1,12-di(N₁′,N₁′-p-chlorophenyldiguanido-N₅,N₅′)dodecane dihydrochloride; 1,6-di(N₁,N₁′-o-chlorophenyldiguanido-N₅,N₅′)hexane dihydrochloride;1,6-di(N₁,N₁′-p-chlorophenyldiguanido-N₅,N₅′)-hexane tetrahydrochloride;and mixtures thereof. As stated hereinbefore, the bis biguanide ofchoice is chlorhexidine its salts, e.g., digluconate, dihydrochloride,diacetate, and mixtures thereof.

The surfactants, when added to the antimicrobials tend to provideimproved antimicrobial action. This is especially true for the siloxanesurfactants, and especially when the siloxane surfactants are combinedwith the chlorhexidine antimicrobial actives.

Aminocarboxylate Chelators

Chelators, e.g., ethylenediaminetetraacetic acid (EDTA),hydroxyethylene-diaminetriacetic acid, diethylenetriaminepentaaceticacid, and other aminocarboxylate chelators, and mixtures thereof, andtheir salts, and mixtures thereof, can optionally be used to increaseantimicrobial and preservative effectiveness against Gram-negativebacteria, especially Pseudomonas species. Although sensitivity to EDTAand other aminocarboxylate chelators is mainly a characteristic ofPseudomonas species, other bacterial species highly susceptible tochelators include Achromobacter, Alcaligenes, Azotobacter, Escherichia,Salmonella, Spirillum, and Vibrio. Other groups of organisms also showincreased sensitivities to these chelators, including fungi and yeasts.Furthermore, aminocarboxylate chelators can help, e.g., maintainingproduct clarity, protecting fragrance and perfume components, andpreventing rancidity and off odors.

Although these aminocarboxylate chelators may not be potent biocides intheir own right, they function as potentiators for improving theperformance of other antimicrobials/preservatives in the compositions ofthe present invention. Aminocarboxylate chelators can potentiate theperformance of many of the cationic, anionic, and nonionicantimicrobials/preservatives, phenolic compounds, and isothiazolinones,that are used as antimicrobials/preservatives in the composition of thepresent invention. Nonlimiting examples of cationicantimicrobials/preservatives potentiated by aminocarboxylate chelatorsin solutions are chlorhexidine salts (including digluconate, diacetate,and dihydrochloride salts), and Quaternium-15, also known as Dowicil200, Dowicide Q, Preventol D1, benzalkonium chloride, cetrimonium,myristalkonium chloride, cetylpyridinium chloride, lauryl pyridiniumchloride, and the like. Nonlimiting examples of useful anionicantimicrobials/preservatives which are enhanced by aminocarboxylatechelators are sorbic acid and potassium sorbate. Nonlimiting examples ofuseful nonionic antimicrobials/preservatives which are potentiated byaminocarboxylate chelators are DMDM hydantoin, phenethyl alcohol,monolaurin, imidazolidinyl urea, and Bronopol(2-bromo-2-nitropropane-1,3-diol).

Examples of useful phenolic antimicrobials/preservatives potentiated bythese chelators are chloroxylenol, phenol, tert-butyl hydroxyanisole,salicylic acid, resorcinol, and sodium o-phenyl phenate. Nonlimitingexamples of isothiazolinone antimicrobials/preservatives which areenhanced by aminocarboxylate chelators are Kathon, Proxel and Promexal.

The optional chelators are present in the compositions of this inventionat levels of, typically, from about 0.01% to about 0.3%, more preferablyfrom about 0.02% to about 0.1%, most preferably from about 0.02% toabout 0.05% by weight of the usage compositions to provide antimicrobialefficacy in this invention.

Free, uncomplexed aminocarboxylate chelators are required to potentiatethe efficacy of the antimicrobials. Thus, when excess alkaline earth(especially calcium and magnesium) and transitional metals (iron,manganese, copper, and others) are present, free chelators are notavailable and antimicrobial potentiation is not observed. In the casewhere significant water hardness or transitional metals are available orwhere product esthetics require a specified chelator level, higherlevels may be required to allow for the availability of free,uncomplexed aminocarboxylate chelators to function asantimicrobial/preservative potentiators.

Antimicrobial Preservative

Optionally, but preferably, an antimicrobial preservative can be addedto the composition of the present invention, preferably solubilized,water-soluble, antimicrobial preservative, to protect the fabric carepolysaccharide with globular structure and/or other easily degradableorganic ingredients such as cyclodextrin, because these molecules aremade up, e.g., of varying numbers of glucose units which can make them aprime breeding ground for certain microorganisms, especially when inaqueous compositions. This drawback can lead to the problem of storagestability of fabric care solutions for any significant length of time.Contamination by certain microorganisms with subsequent microbial growthcan result in an unsightly and/or malodorous solution. Because microbialgrowth in the fabric care solutions is highly objectionable when itoccurs, it is highly preferable to include an antimicrobialpreservative, preferably solubilized, water-soluble, antimicrobialpreservative, which is effective for inhibiting and/or regulatingmicrobial growth in order to increase storage stability of thepreferably clear, aqueous odor-absorbing solution containing the fabriccare polysaccharide with globular structure.

It is preferable to use a broad spectrum preservative, e.g., one that iseffective on both bacteria (both gram positive and gram negative) andfungi. A limited spectrum preservative, e.g., one that is only effectiveon a single group of microorganisms, e.g., fungi, can be used incombination with a broad spectrum preservative or other limited spectrumpreservatives with complimentary and/or supplementary activity. Amixture of broad spectrum preservatives can also be used. In some caseswhere a specific group of microbial contaminants is problematic (such asGram negatives), aminocarboxylate chelators can be used alone or aspotentiators in conjunction with other preservatives. These chelatorswhich include, e.g., ethylenediaminetetraacetic acid (EDTA),hydroxyethylenediaminetriacetic acid, diethylenetriaminepentaaceticacid, and other aminocarboxylate chelators, and mixtures thereof, andtheir salts, and mixtures thereof, can increase preservativeeffectiveness against Gram-negative bacteria, especially Pseudomonasspecies.

Antimicrobial preservatives useful in the present invention includebiocidal compounds, i.e., substances that kill microorganisms, orbiostatic compounds, i.e., substances that inhibit and/or regulate thegrowth of microorganisms. Suitable preservatives are disclosed in U.S.Pat. Nos. 5,534,165; 5,578,563; 5,663,134; 5,668,097; 5,670,475; and5,714,137, Trinh et al. issued Jul. 9, 1996; Nov. 26, 1996; Sep. 2,1997; Sep. 16, 1997; Sep. 23, 1997; and Feb. 3, 1998 respectively, allof said patents being incorporated hereinbefore by reference. Manyantimicrobial preservatives are given under the section on AntimicrobialActive given herein above. Water insoluble antimicrobial preservativessuch as paraben and triclosan are useful in the fabric care compositionsof the present invention, but they require the use of a solubilizer, anemulsifier, a dispersing agent, or the like, such as a surfactant and/orcyclodextrin to effectively distribute said preservative in the liquidcomposition. Preferred antimicrobial preservatives are those that arewater-soluble and are effective at low levels. Water-solublepreservatives useful in the present invention are those that have asolubility in water of at least about 0.3 g per 100 ml of water, i.e.,greater than about 0.3% at room temperature, preferably greater thanabout 0.5% at room temperature.

The water-soluble antimicrobial preservative in the present invention isincluded at an effective amount. The term “effective amount” as hereindefined means a level sufficient to prevent spoilage, or prevent growthof inadvertently added microorganisms, for a specific period of time. Inother words, the preservative is not being used to kill microorganismson the surface onto which the composition is deposited in order toeliminate odors produced by microorganisms. Instead, it is preferablybeing used to prevent spoilage of the fabric care polysaccharide withglobular structure solution in order to increase the shelf-life of thecomposition. Preferred levels of preservative are from about 0.0001% toabout 0.5%, more preferably from about 0.0002% to about 0.2%, mostpreferably from about 0.0003% to about 0.1%, by weight of the usagecomposition.

The preservative can be any organic preservative material which will notcause damage to fabric appearance, e.g., discoloration, coloration,bleaching. Preferred water-soluble preservatives include organic sulfurcompounds, halogenated compounds, cyclic organic nitrogen compounds, lowmolecular weight aldehydes, quaternary ammonium compounds, dehydroaceticacid, phenyl and phenolic compounds, and mixtures thereof.

The preservatives of the present invention can be used in mixtures inorder to control a broad range of microorganisms.

Bacteriostatic effects can sometimes be obtained for aqueouscompositions by adjusting the composition pH to an acid pH, e.g., lessthan about pH 4, preferably less than about pH 3, or a basic pH, e.g.,greater than about 10, preferably greater than about 11.

Fabric Softening Active

The fabric care composition herein can optionally contain fabricsoftening active. A liquid rinse-added composition typically containsfrom about 1% to about 75%, preferably from about 2% to about 65%, morepreferably from about 3% to about 45%, and even more preferably fromabout 4% to about 35% by weight of the composition, of a fabric softeneractive. For a dryer-added composition, the levels are from about 1% toabout 99%, preferably from about 10% to about 80%, more preferably fromabout 20% to about 70%, and even more preferably from about 25% to about60% of fabric softening active. For a spray-on composition the levelsare from about 0.05% to about 10%, preferably from about 0.1% to about7%, more preferably from about 0.5% to about 5%.

The rinse-added fabric care compositions containing fabric softeningactives herein can comprise liquid compositions that can be eitherdispersions or clear.

Dispersion Compositions

Stable “dispersion” compositions can be prepared like those disclosed inU.S. Pat. No. 4,661,269, issued Apr. 28, 1987, to T. Trinh et al., andin U.S. Pat. No. 5,545,340, issued Aug. 13, 1996, to Wahl et al., saidpatents being incorporated herein by reference. Suitable optionalcomponents in addition to the softening active are disclosedhereinafter. The dispersion liquid compositions herein can be bothdilute and concentrated, but are preferably concentrated.

Clear Compositions

Preferred compositions are concentrate and clear, comprising:

-   I. from about 2% to about 80%, preferably from about 13% to about    75%, more preferably from about 17% to about 70%, and even more    preferably from about 19% to about 65%, by weight of the    composition, of fabric softening active, having a phase transition    temperature of less than about 50° C., preferably less than about    35° C., more preferably less than about 20° C., and even more    preferably less than about 0° C., preferably being biodegradable    fabric softening active containing unsaturated alkyl groups and/or    branched fatty alkyl groups, said unsaturated alkyl groups having an    average Iodine Value (IV) of at least about 40, a level of    polyunsaturation preferably being at least about 5%, and with the    level of C18:3 acyl groups in the starting fatty acyl source    feedstock for making the said softening active preferably being less    than about 1% by weight.-   II. less than about 40%, preferably from about 10% to about 35%,    more preferably from about 12% to about 25%, and even more    preferably from about 14% to about 20%, by weight of the composition    of principal solvent having a ClogP of from about −2.0 to about 2.6,    preferably from about −1.7 to about 1.7, and more preferably from    about −1.0 to about 1.0, and preferably having some degree of    asymmetry; optionally, but preferably, an effective amount,    sufficient to improve clarity, of low molecular weight water soluble    solvents like ethanol, isopropanol, propylene glycol,    1,3-propanediol, propylene carbonate, etc.; and optionally, but    preferably, an effective amount to improve clarity, of water soluble    calcium and/or magnesium salt, preferably chloride;-   II. optionally, but highly preferred for clear/translucent    compositions, at least an effective level of principal solvent    preferably having a ClogP of from about −2.0 to about 2.6, more    preferably from about −1.7 to about 1.6, and even more preferably    from about 1.0 to about 1.0, as defined hereinafter, typically at a    level that is less than about 40%, preferably from about 1% to about    25%, more preferably from about 3% to about 8% by weight of the    composition;-   III. optionally, but preferably, from about 0.1% to about 10% by    weight, preferably from about 0.75% to about 2.5% by weight of the    composition, and more preferably from about 1% to about 2% by weight    of the composition of electrolyte as defined hereinafter;-   IV. optionally, but preferably, from 0% to about 15%, preferably    from about 0.1% to about 7%, and more preferably from about 1% to    about 6%, by weight of the composition of phase stabilizer,    preferably surfactant containing alkoxylation, and also preferably    having an HLB of from about 8 to about 20, more preferably from    about 10 to about 18, and even more preferably from about 11 to    about 15; and-   V. the balance water, minor ingredients and/or water soluble    solvents.

The preferred principal solvent and/or electrolyte levels, as well asthe identity of the principal solvent, are selected normally accordingto the level and identity of the softener. Preferred levels and identityof principal solvent, electrolyte, and phase stabilizer which will yieldclear stable compositions are taught in copending U.S. patentapplication Ser. No. 09/309,128, filed May 10, 1999, Frankenbach et al.,incorporated herein by reference.

ClogP of a solvent is the calculated logarithm to the base 10 of theoctanol/water partition coefficient (P) of said solvent. ClogP valuesare conveniently calculated by the “CLOGP” program, available fromDaylight Chemical Information Systems, Inc. (Daylight CIS), Irvine,Calif. The “calculated logP” (ClogP) is determined by the fragmentapproach of Hansch and Leo (cf., A. Leo, in Comprehensive MedicinalChemistry, Vol. 4, C. Hansch, P. G. Sammens, J. B. Taylor and C. A.Ramsden, Eds., p. 295, Pergamon Press, 1990, incorporated herein byreference). The fragment approach is based on the chemical structure ofeach ingredient, and takes into account the numbers and types of atoms,the atom connectivity, and chemical bonding. Other methods that can beused to compute ClogP include, e.g., Crippen's fragmentation method asdisclosed in J. Chem. Inf. Comput. Sci., 27, 21 (1987); Viswanadhan'sfragmentation method as disclose in J. Chem. Inf. Comput. Sci., 29, 163(1989); and Broto's method as disclosed in Eur. J. Med. Chem.—Chim.Theor., 19, 71 (1984).

Fabric Softening Actives

Fabric softening actives that can be used herein are disclosed, at leastgenerically for the basic structures, in U.S. Pat. No. 3,408,361,Mannheimer, issued Oct. 29, 1968; U.S. Pat. No. 4,709,045; Kubo et al.,issued Nov. 24, 1987; U.S. Pat. No. 4,233,451, Pracht et al., issuedNov. 11, 1980; U.S. Pat. No. 4,127,489, Pracht et al., issued Nov. 28,1979; U.S. Pat. No. 3,689,424, Berg et al., issued Sep. 5, 1972; U.S.Pat. No. 4,128,485, Baumann et al., issued Dec. 5, 1978; U.S. Pat. No.4,161,604, Elster et al., issued Jul. 17, 1979; U.S. Pat. No. 4,189,593,Wechsler et al., issued Feb. 19, 1980; U.S. Pat. No. 4,339,391, Hoffmanet al., issued Jul. 13, 1982 U.S. Pat. No. 3,861,870, Edwards and Diehl;U.S. Pat. No. 4,308,151, Cambre; U.S. Pat. No. 3,886,075, Bernardino;U.S. Pat. No. 4,233,164, Davis; U.S. Pat. No. 4,401,578, Verbruggen;U.S. Pat. No. 3,974,076, Wiersema and Rieke; U.S. Pat. No. 4,237,016,Rudkin, Clint, and Young; U.S. Pat. No. 4,885,102, Yamamura et al.,issued Dec. 5, 1989; U.S. Pat. No. 4,937,008, Yamamura et al., issuedJun. 26, 1990; and U.S. Pat. No. 5,133,885, Contor et al., issued Jul.28, 1992; Case 4768C, Trinh et al.; and European patent applications91/336,267, Rutzen et a.l. and 91/423,894, Contor et al. andInternational Patent WO 91/01295, Trius et al., published Feb. 7, 1991,all of said patents and applications being incorporated herein byreference.

Other preferred fabric softening actives for liquid rinse-addedcompositions are disclosed in U.S. Pat. No. 4,661,269, issued Apr. 28,1987, to T. Trinh, E. H. Wahl, D. M. Swartley and R. L. Hemingway.Biodegradable ester and/or amide linked fabric softening actives aredisclosed, e.g., in U.S. Pat. No. 5,545,340, issued Aug. 13, 1996, toWahl et al. Biodegradable unsaturated ester and/or amide linked fabricsoftening actives in concentrated clear compositions are disclosed inU.S. Pat. No. 5,759,990, issued Jun. 2, 1998 in the names of Wahl,Tordil, Trinh, Carr, Keys, and Meyer, and in U.S. Pat. No. 5,747,443,issued May 5, 1998 in the names of Wahl, Trinh, Gosselink, Letton, andSivik. All said patents are incorporated herein by reference. Examplesof suitable amine softening actives that can be used in the presentinvention are disclosed in PCT application WO 99/06509, K. A. Grimm, D.R. Bacon, T. Trinh, E. H. Wahl, and H. B. Tordil, published on Feb. 11,1999, said application being incorporated herein by reference.

Any fabric softening active, including quaternary and non-quaternarysoftening actives, with saturated, partially saturated, unsaturatedan/or highly unsaturated, with straight, linear alkyl chains and/orbranched alkyl groups, can be use in the rinse-added fabric carecomposition of the present invention. Biodegradable fabric softeningactives are preferred.

A preferred fabric care composition herein uses fabric softening activewith highly unsaturated and/or branched hydrophobic chains, preferablybiodegradable, selected from the highly unsaturated and/or branchedfabric softening actives, and mixtures thereof. These highly unsaturatedand/or branched fabric softening actives have the required propertiesfor permitting high usage levels to provide additional fabric appearancebenefits, including recovery of fabric color appearance, improved colorintegrity, and anti-wrinkling benefits. Fabric softening actives withsaturated and/or low degree of unsaturation, e.g., Iodine Value of lessthan about 10, and fabric softening actives with unsaturated chainshaving the trans configuration, can normally provide a better softeningperformance per unit weight, but are more difficult to concentrate, thuscan be used in compositions with lower levels of fabric softeningactive, typically below about 30%, preferably below 25%, more preferablybelow 20%, by weight of the composition.

Preferred fabric softening actives of the invention comprise a majorityof compounds as follows:

Diester Quaternary Ammonium Fabric Softening Active Compound (DEQA)

-   -   (1) The first type of DEQA preferably comprises, as the        principal active, compounds of the formula        {R_(4-m)—N⁺—[(CH₂)_(n)—Y—R¹]_(m)}A⁻        wherein each R substituent is either hydrogen, a short chain        C₁–C₆, preferably C₁–C₃ alkyl or hydroxyalkyl group, e.g.,        methyl (most preferred), ethyl, propyl, hydroxyethyl, and the        like, poly (C₂₋₃alkoxy) preferably polyethoxy group, benzyl, or        mixtures thereof; each m is 2 or 3; each n is from 1 to about 4;        each Y is —O—(O)C—, —C(O)—O—, —NR—C(O)—, or —C(O)—NR—; the sum        of carbons in each R¹, plus one when Y is —O—(O)C— or —NR—C(O)—,        is C₁₂–C₂₂, preferably C₁₄–C₂₀, with each R¹ being a        hydrocarbyl, or substituted hydrocarbyl group, and A⁻ can be any        softener-compatible anion, preferably, chloride, bromide,        methylsulfate, ethylsulfate, sulfate, and nitrate, more        preferably chloride or methyl sulfate. (As used herein, the        “percent of softening active” containing a given R¹ group is        based upon taking a percentage of the total active based upon        the percentage that the given R¹ group is, of the total R¹        groups present.)    -   (2) A second type of DEQA active has the general formula:        [R₃N⁺CH₂CH(YR¹)(CH₂YR¹)]A⁻        wherein each Y, R, R¹, and A⁻ have the same meanings as before.        Such compounds include those having the formula:        [CH₃]₃ N⁽⁺⁾[CH₂CH(CH₂O(O)CR¹)O(O)CR¹]Cl⁽⁻⁾        where each R is a methyl or ethyl group and preferably each R¹        is in the range of C₁₅ to C₁₉.

These types of agents and general methods of making them are disclosedin U.S. Pat. No. 4,137,180, Naik et al., issued Jan. 30, 1979, which isincorporated herein by reference. An example of a preferred DEQA offormula (2) is the “propyl” ester quaternary ammonium fabric softeningactive having the formula 1,2-di(acyloxy)-3-trimethylammoniopropanechloride, where the acyl is the same as that of FA¹ mixture disclosedhereinafter.

These biodegradable quaternary ammonium fabric softening compoundspreferably contain the group C(O)R¹ which is derived, primarily fromsaturated fatty acids, such as stearic acid, but more preferably derivedfrom partially saturated fatty acids and/or partially hydrogenated fattyacids from natural sources, e.g., derived from animal fat, such astallow fatty acids. Also preferred are unsaturated fatty acids, e.g.,oleic acid, and polyunsaturated fatty acids, such as those derived fromvegetable oils, such as, canola oil, safflower oil, peanut oil,sunflower oil, corn oil, soybean oil, tall oil, rice bran oil, etc.Non-limiting examples of fatty acids (FA) are listed in U.S. Pat. No.5,759,990 at column 4, lines 45–66. Fabric softening actives containingunsaturated and polyunsaturated fatty acids are preferred in formulatingconcentrated, clear fabric softening compositions of the presentinvention.

Mixtures of fatty acids can be used, and are preferred. Nonlimitingexamples of fatty acids that can be blended, to form fatty acid mixtures(FA's) of this invention are as follows:

Fatty Acyl Group FA¹ FA² FA³ C₁₄ 0 0 1 C₁₆ 3 11 25 C₁₈ 3 4 20 C14:1 0 00 C16:1 1 1 0 C18:1 79 27 45 C18:2 13 50 6 C18:3 1 7 0 Unknowns 0 0 3Total 100 100 100 IV 99 125–138 56 cis/trans (C18:1) 5–6 Not Available 7TPU 14 57 6

FA¹ is a partially hydrogenated fatty acid prepared from canola oil, FA²is a fatty acid prepared from soy bean oil, and FA³ is a slightlyhydrogenated tallow fatty acid.

Iodine Value (referred to as “IV” herein) is used to define the level ofunsaturation of a fatty acid. As used herein, Iodine Value of the“parent” fatty acid, or “corresponding” fatty acid that the R¹ group isderived from, is also used to define the level of unsaturation of afabric softening active. The IV of the parent fatty acids of these R¹group is from about 0 to about 140, more preferably from about 40 toabout 130, on the average. For concentrate, clear compositions, The IVis preferably from about 70 to about 140, more preferably from about 80to about 130, and even more preferably from about 90 to about 115, onthe average.

It is preferred that at least a majority of the fatty acyl groups areunsaturated, e.g., from about 50% to 100%, preferably from about 55% toabout 100%, more preferably from about 60% to about 100%. The cis/transratio for the unsaturated fatty acyl groups is important, with apreferred cis/trans ratio of from 1:1 to about 50:1, the minimum being1:1, preferably at least 3:1, and more preferably from about 4:1 toabout 20:1.

The long chain hydrocabon groups can also comprise branched chains,e.g., from isostearic acid, for at least part of the groups. The totalof active represented by the branched chain groups, when they arepresent, is typically from about 1% to about 100%, preferably from about10% to about 70%, more preferably from about 20% to about 50%.

The unsaturated, including the polyunsaturated, fatty acyl groups notonly provide surprisingly effective softening, but also provide betterabsorbency characteristics, good antistatic characteristics, andsuperior recovery after freezing and thawing. These highlyunsaturated/branched materials provide excellent softening whileminimizing loss of water absorbency and “greasy” fabric feel. These twocharacteristics allow one to use higher levels of softening active thanwould be ordinarily desirable, which provides several additionalbenefits, including noticeable color maintenance, protection, and/orrecovery for colored fabrics, especially colored cotton and cotton blendfabrics, improved anti-wrinkling benefit, improved fiber integrity,i.e., less damage to fabrics, improved antistatic benefits, and a highlevel of softness.

The highly unsaturated materials are also easier to formulate intoconcentrated premixes that maintain their low viscosity and aretherefore easier to process, e.g., pump, mixing, etc. These highlyunsaturated materials with only a low amount of solvent that normally isassociated with such materials, i.e., from about 5% to about 20%,preferably from about 8% to about 25%, more preferably from about 10% toabout 20%, weight of the total softening active/solvent mixture, arealso easier to formulate into concentrated, stable dispersioncompositions of the present invention, even at ambient temperatures.

It will be understood that substituents R and R¹ can optionally besubstituted with various groups such as alkoxyl or hydroxyl groups, solong as the R¹ groups maintain their basically hydrophobic character.The preferred compounds can be considered to be biodegradable diestervariations of ditallow dimethyl ammonium chloride (hereinafter referredto as “DTDMAC”), which is a widely used fabric softening active. Apreferred long chain DEQA is the DEQA prepared from sources containinghigh levels of polyunsaturation, i.e.,N,N-di(acyl-oxyethyl)-N,N-dimethyl ammonium chloride, where the acyl isderived from fatty acids containing sufficient polyunsaturation.

As used herein, when the diester (m=2) is specified, it can include themonoester (m=1) and/or triester (m=3) that is present. Preferably, atleast about 70% of the DEQA is in the diester form, and from 0% to about30% can be DEQA monoester. For softening, under no/low detergentcarry-over laundry conditions the percentage of monoester should be aslow as possible, preferably no more than about 15%. However, under high,anionic detergent surfactant or detergent builder carry-over conditions,some monoester or monoamide can be preferred. The overall ratios ofdiester to monoester, or diamide to monoamide, are from about 100:1 toabout 2:1, preferably from about 50:1 to about 5:1, more preferably fromabout 13:1 to about 8:1. Under high detergent carry-over conditions, thedi/monoester ratio is preferably about 11:1. The level of monoester, ormonoamide, present can be controlled in manufacturing the DEQA.

The above compounds, used as the biodegradable quaternized ester-amineor amido-amine, softening material in the practice of this invention,can be prepared using standard reaction chemistry. In one synthesis of adiester variation of DTDMAC, an amine of the formula RN(CH₂CH₂OH)₂ isesterified at both hydroxyl groups with an acid chloride of the formulaR¹C(O)Cl, then quaternized with an alkyl halide, RX, to yield thedesired reaction product (wherein R and R¹ are as defined hereinbefore).However, it will be appreciated by those skilled in the chemical artsthat this reaction sequence allows a broad selection of agents to beprepared.

Yet another DEQA softening active that is suitable for the formulationof the concentrated, liquid fabric care compositions of the presentinvention, has the above formula (1) wherein one R group is a C₁₋₄hydroxy alkyl group, or polyalkoxy group, preferably hydroxy alky, morepreferably hydroxyethyl, group. An example of such a hydroxyethyl esteractive is di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methylsulfate, where the acyl is derived from the fatty acids describedhereinbefore, e.g., oleic acid. Such DEQA is a quaternized product ofcondensation between: (a)—a fraction of saturated or unsaturated, linearor branched fatty acids, or of derivatives of said acids, said fattyacids or derivatives each possessing a hydrocarbon chain in which thenumber of atoms is between 5 and 21, and (b) triethanolamine,characterized in that said condensation product has an acid value,measured by titration of the condensation product with a standard KOHsolution against a phenolphthalein indicator, of less than about 6.5.The acid value is preferably less than or equal to about 5, morepreferably less than about 3. Indeed, the lower the AV, the bettersoftness performance is obtained.

The acid value is determined by titration of the condensation productwith a standard KOH solution against a phenolphthalein indicatoraccording to ISO#53402. The AV is expressed as mg KOH/g of thecondensation product.

For optimum softness benefit, it is preferred that the reactants arepresent in a molar ratio of fatty acid fraction to triethanolamine offrom about 1:1 to about 2.5:1.

It has also been found that the optimum softness performance is alsoaffected by the detergent carry-over laundry conditions, and moreespecially by the presence of the anionic surfactant in the solution inwhich the softening composition is used. Indeed, the presence of anionicsurfactant that is usually carried over from the wash will interact withthe softener compound, thereby reducing its performance. Thus, dependingon usage conditions, the mole ratio of fatty acid/triethanolamine can becritical. Accordingly, where no rinse occurs between the wash cycle andthe rinse cycle containing the softening compound, a high amount ofanionic surfactant will be carried over in the rinse cycle containingthe softening compound. In this instance, it has been found that a fattyacid fraction/triethanolamine mole ratio of about 1.4:1 to about 1.8:1is preferred. By high amount of anionic surfactant, it is meant that thepresence of anionic in the rinse cycle at a level such that the molarratio anionic surfactant/cationic softener compound of the invention isat least about 1/10.

The compositions can also contain medium-chain cationic ammonium fabricsoftening compound, including DEQAs having the above formula (1) and/orformula (2), below, wherein:

-   -   each Y is —O—(O)C—, —(R)N—(O)C—, —C(O)—N(R)—, or —C(O)—O—,        preferably —O—(O)C—;    -   m is 2 or 3, preferably 2;    -   each n is 1 to 4, preferably 2;    -   each R is as defined hereinbefore;    -   each R¹, or YR¹ hydrophobic group is a saturated, C₈–C₁₄,        preferably a C₁₂₋₁₄ hydrocarbyl, or substituted hydrocarbyl        substituent (the IV is preferably about 10 or less, more        preferably less than about 5), [The sum of the carbons in the        hydrophobic group is the number of carbon atoms in the R¹ group,        or in the YR¹ group when Y is —O—(O)C— or —(R)N—(O)C—.] and the        counterion, A⁻, is the same as above. Preferably A⁻ does not        include phosphate salts.

The saturated C₈–C₁₄ fatty acyl groups can be pure derivatives or can bemixed chainlengths.

Suitable fatty acid sources for said fatty acyl groups are coco, lauric,caprylic, and capric acids.

For C₁₂–C₁₄ (or C₁₁–C₁₃) hydrocarbyl groups, the groups are preferablysaturated, e.g., the IV is preferably less than about 10, preferablyless than about 5.

It will be understood that substituents R and R¹ can optionally besubstituted with various groups such as alkoxyl or hydroxyl groups, andcan be straight, or branched so long as the R¹ groups maintain theirbasically hydrophobic character.

The DEQA actives described hereinabove can contain a low level of thefatty acids which can be unreacted starting material and/or by-productof any partial degradation, e.g., hydrolysis, of the softening activesin the finished compositions. It is preferred that the level of freefatty acid be low, preferably below about 10%, more preferably belowabout 5%, by weight of the softening active.

Other types of fabric softening actives can be used in the rinse-addedfabric care compositions of the present invention:

-   -   (3) The DEQA actives described hereinabove also include the        neutralized amine softening actives wherein at least one R group        is a hydrogen atom. A non-limiting example of actives of this        type is the chloride salt of (unsaturated        alkoyloxyethyl)(unsaturated alkylamidotrimethylene)methylamine.        Other examples of suitable amine softening actives are disclosed        in PCT application WO 99/06509, K. A. Grimm, D. R. Bacon, T.        Trinh, E. H. Wahl, and H. B. Tordil, published on Feb. 11, 1999,        said application being incorporated herein by reference.    -   (4) Polyquaternary Ammonium Softening Actives. Fabric softening        actives carrying more than one positive quaternary ammonium        charge are also useful in the rinse-added compositions of the        present invention. An example of this type of softening active        is that having the formula:        wherein each R is H or a short chain C₁–C₆, preferably C₁–C₃        alkyl or hydroxyalkyl group, e.g., methyl (most preferred),        ethyl, propyl, hydroxyethyl, and the like, benzyl, or (R²        O)₂₋₄H; each R¹ is a C₆–C₂₂, preferably C₁₄–C₂₀ hydrocarbyl, or        substituted hydrocarbyl substituent, preferably C₁₀–C₂₀ alkyl or        alkenyl (unsaturated alkyl, including polyunsaturated alkyl,        also referred to sometimes as “alkylene”), most preferably        C₁₂–C₁₈ alkyl or alkenyl; each R² is a C₁₋₆ alkylene group,        preferably an ethylene group; and A⁻ are defined as below.        Fabric softening actives having the following formula:        wherein R¹ is derived from oleic acid is available from Witco        Company.

The following polyquaternary ammonium compounds are disclosed byreference herein as also suitable for use in this invention: EuropeanPatent Application EP 0,803,498, A1, Robert O. Keys and Floyd E.Friedli, filed Apr. 25, 1997; British Pat. 808,265, issued Jan. 28, 1956to Arnold Hoffman & Co., Incorporated; British Pat. 1,161,552, Koebnerand Potts, issued Aug. 13, 1969; DE 4,203,489 A1, Henkel, published Aug.12, 1993; EP 0,221,855, Topfl, Heinz, and Jorg, issued Nov. 3, 1986; EP0,503,155, Rewo, issued Dec. 20, 1991; EP 0,507,003, Rewo, issued Dec.20, 1991; EPA 0,803,498, published Oct. 29, 1997; French Pat. 2,523,606,Marie-Helene Fraikin, Alan Dillarstone, and Marc Couterau, filed Mar.22, 1983; Japanese Pat. 84-273918, Terumi Kawai and Hiroshi Kitamura,1986; Japanese Pat. 2-011,545, issued to Kao Corp., Jan. 16, 1990; U.S.Pat. No. 3,079,436, Hwa, issued Feb. 26, 1963; U.S. Pat. No. 4,418,054,Green et al., issued Nov. 29, 1983; U.S. Pat. No. 4,721,512, Topfl,Abel, and Binz, issued Jan. 26, 1988; U.S. Pat. No. 4,728,337, Abel,Topfl, and Riehen, issued Mar. 1, 1988; U.S. Pat. No. 4,906,413, Topfland Binz, issued Mar. 6, 1990; U.S. Pat. No. 5,194,667, Oxenrider etal., issued Mar. 16, 1993; U.S. Pat. No. 5,235,082, Hill and Snow,issued Aug. 10, 1993; U.S. Pat. No. 5,670,472, Keys, issued Sep. 23,1997; Weirong Miao, Wei Hou, Lie Chen, and Zongshi Li, Studies onMultifunctional Finishing Agents, Riyong Huaxue Gonye, No. 2, pp. 8–10,1992; Yokagaku, Vol 41, No. 4 (1992); and Disinfection, Sterilization,and Preservation, 4^(th) Edition, published 1991 by Lea & Febiger,Chapter 13, pp. 226–30. All of these references are incorporated herein,in their entirety, by reference. The products formed by quaternizationof reaction products of fatty acid with N,N,N′,N′,tetraakis(hydroxyethyl)-1,6-diaminohexane are also suitable for thisinvention.

-   -   (5) Softening active having the formula:        R_(4-m)—N⁽⁺⁾—R¹ _(m)A⁻        wherein each m is 2 or 3, each R¹ is a C₆–C₂₂, preferably        C₁₄–C₂₀, but no more than one being less than about C₁₂ and then        the other is at least about 16, hydrocarbyl, or substituted        hydrocarbyl substituent, preferably C₁₀–C₂₀ alkyl or alkenyl,        most preferably C₁₂–C₁₈ alkyl or alkenyl, and where the Iodine        Value of a fatty acid containing this R¹ group is from 0 to        about 140, more preferably from about 40 to about 130; with a        cis/trans ratio of from about 1:1 to about 50:1, the minimum        being 1:1, preferably from about 2:1 to about 40:1, more        preferably from about 3:1 to about 30:1, and even more        preferably from about 4:1 to about 20:1; each R¹ can also be a        branched chain C₁₄–C₂₂ alkyl group, preferably a branched chain        C₁₆–C₁₈ group; each R is H or a short chain C₁–C₆, preferably        C₁–C₃ alkyl or hydroxyalkyl group, e.g., methyl (most        preferred), ethyl, propyl, hydroxyethyl, and the like, benzyl,        or (R² O)₂₋₄H; and A⁻ is a softening active compatible anion,        preferably, chloride, bromide, methylsulfate, ethylsulfate,        sulfate, and nitrate, more preferably chloride and methyl        sulfate;    -   (6) Softening active having the formula:        wherein each R, R¹, and A⁻ have the definitions given above;        each R² is a C₁₋₆ alkylene group, preferably an ethylene group;        and G is an oxygen atom or an —NR— group;    -   (7) Softening active having the formula:        wherein R¹, R² and G are defined as above;    -   (8) Reaction products of substantially unsaturated and/or        branched chain higher fatty acids with dialkylenetriamines in,        e.g., a molecular ratio of about 2:1, said reaction products        containing compounds of the formula:        R¹—C(O)—NH—R²—NH—R³—NH—C(O)—R¹        wherein R¹, R² are defined as above, and each R³ is a C₁₋₆        alkylene group, preferably an ethylene group;    -   (9) Softening active having the formula:        [R¹—C(O)—NR—R²—N(R)₂—R³—NR—C(O)—R¹]⁺A⁻        wherein R, R¹, R², R³ and A⁻ are defined as above;    -   (10) The reaction product of substantially unsaturated and/or        branched chain higher fatty acid with        hydroxyalkylalkylenediamines in a molecular ratio of about 2:1,        said reaction products containing compounds of the formula:        R¹—C(O)—NH—R²—N(R³OH)—C(O)—R¹        wherein R¹, R² and R³ are defined as above; and    -   (11) Mixtures thereof.

Examples of Compound (5) are dialkylenedimethylammonium salts such asdicanoladimethylammonium chloride, dicanoladimethylammoniummethylsulfate, di(partially hydrogenated soybean, cis/trans ratio ofabout 4:1)dimethylammonium chloride, dioleyldimethylammonium chloride.Dioleyldimethylammonium chloride and di(canola)dimethylammonium chlorideare preferred. An example of commercially availabledialkylenedimethylammonium salts usable in the present invention isdioleyldimethylammonium chloride available from Witco Corporation underthe trade name Adogen® 472.

An example of Compound (6) is1-methyl-1-oleylamidoethyl-2-oleylimidazolinium methylsulfate wherein R¹is an acyclic aliphatic C₁₅–C₁₇ hydrocarbon group, R² is an ethylenegroup, G is a NH group, R⁵ is a methyl group and A⁻ is a methyl sulfateanion, available commercially from the Witco Corporation under the tradename Varisoft® 3690.

An example of Compound (7) is 1-oleylamidoethyl-2-oleylimidazolinewherein R¹ is an acyclic aliphatic C₁₅–C₁₇ hydrocarbon group, R² is anethylene group, and G is a NH group.

An example of Compound (8) is reaction products of oleic acids withdiethylenetriamine in a molecular ratio of about 2:1, said reactionproduct mixture containing N,N″-dioleoyldiethylenetriamine with theformula:R¹—C(O)—NH—CH₂CH₂—NH—CH₂CH₂—NH—C(O)—R¹wherein R¹—C(O) is oleoyl group of a commercially available oleic acidderived from a vegetable or animal source, such as Emersol® 223LL orEmersol® 7021, available from Henkel Corporation, and R² and R³ aredivalent ethylene groups.

An example of Compound (9) is a difatty amidoamine based softeningactive having the formula:[R¹—C(O)—NH—CH₂CH₂—N(CH₃)(CH₂CH₂OH)—CH₂CH₂—NH—C(O)—R¹]⁺CH₃SO₄ ⁻wherein R¹—C(O) is oleoyl group, available commercially from the WitcoCorporation under the trade name Varisoft® 222LT.

An example of Compound (10) is reaction products of oleic acids withN-2-hydroxyethylethylenediamine in a molecular ratio of about 2:1, saidreaction product mixture containing a compound of the formula:R¹—C(O)—NH—CH₂CH₂—N(CH₂CH₂OH)—C(O)—R¹wherein R¹—C(O) is oleoyl group of a commercially available oleic acidderived from a vegetable or animal source, such as Emersol® 223LL orEmersol® 7021, available from Henkel Corporation.

wherein R¹, R² and A⁻ are defined as herein above; and

-   -   (17) Monoalkyl diquaternary salts, e.g., that having the        formula:        A⁻[R¹—N⁽⁺⁾(R)₂—R²N⁽⁺⁾(R)₃]A⁻        wherein R, R¹, R² and A⁻ are defined as herein above; and    -   (18) Mixtures thereof.

Examples of Compound (12) are the monoalkenyltrimethylammonium saltssuch as monooleyltrimethylammonium chloride, monocanolatrimethylammoniumchloride, and soyatrimethylammonium chloride. Monooleyltrimethylammoniumchloride and monocanolatrimethylammonium chloride are preferred. Otherexamples of Compound (12) are soyatrimethylammonium chloride availablefrom Witco Corporation under the trade name Adogen® 415,erucyltrimethylammonium chloride wherein R¹ is a C₂₂ hydrocarbon groupderived from a natural source; soyadimethylethylammonium ethylsulfatewherein R¹ is a C₁₆–C₁₈ hydrocarbon group, R⁵ is a methyl group, R⁶ isan ethyl group, and A⁻ is an ethylsulfate anion; and methylbis(2-hydroxyethyl)oleylammonium chloride wherein R¹ is a C₁₈hydrocarbon group, R⁵ is a 2-hydroxyethyl group and R⁶ is a methylgroup.

An example of Compound (14) is1-ethyl-1-(2-hydroxyethyl)-2-isoheptadecylimidazolinium ethylsulfatewherein R¹ is a C₁₇ hydrocarbon group, R² is an ethylene group, R⁵ is anethyl group, and A⁻ is an ethylsulfate anion.

An example of Compound (17) is N-tallow pentamethyl propane diammoniumdichloride, with the formula:Cl⁻[(tallowalkyl)—N⁽⁺⁾(CH₃)₂—CH₂—CH₂—N⁽⁺⁾(CH₃)₃]Cl⁻available from Witco Corporation under the trade name Adogen® 477.Anion A

In the cationic nitrogenous salts herein, the anion A⁻, which is anysoftening active compatible anion, provides electrical neutrality. Mostoften, the anion used to provide electrical neutrality in these salts isfrom a strong acid, especially a halide, such as chloride,methylsulfate, bromide, or iodide. However, other anions can be used,such as ethylsulfate, acetate, formate, sulfate, carbonate, and thelike. Chloride and methylsulfate are preferred herein as anion A.

Dryer-Added Compositions. The fabric softening compound, or compounds,which are useful in the dryer-added fabric care composition can beselected from cationic, nonionic, amphoteric and/or anionic fabricsoftening compound.

The typical cationic fabric softening compounds include thewater-insoluble quaternary-ammonium fabric softening actives, the mostcommonly used having been di(long alkylchain)dimethylammonium (C1–C4alkyl)sulfate or chloride, preferably the methyl sulfate, compoundsincluding the following:

-   1) di(tallowalkyl)dimethylammonium methyl sulfate (DTDMAMS);-   2) di(hydrogenated tallowalkyl)dimethylammonium methyl sulfate;-   3) di(hydrogenated tallowalkyl)dimethylammonium chloride (DTDMAC);-   4) distearyldimethylammonium methyl sulfate;-   5) dioleyldimethylammonium methyl sulfate;-   6) dipalmitylhydroxyethylmethylammonium methyl sulfate;-   7) stearylbenzyldimethylammonium methyl sulfate;-   8) tallowalkyltrimethylammonium methyl sulfate;-   9) (hydrogenated tallowalkyl)trimethylammonium methyl sulfate;-   10) (C₁₂₋₁₄ alkyl)hydroxyethyldimethylammonium methyl sulfate;-   11) (C₁₂₋₁₈ alkyl)di(hydroxyethyl)methylammonium methyl sulfate;-   12) di(stearoyloxyethyl)dimethylammonium chloride;-   13) di(tallowoyloxyethyl)dimethylammonium methyl sulfate;-   14) ditallowalkylimidazolinium methyl sulfate;-   15) 1-(2-tallowylamidoethyl)-2-tallowylimidazolinium methyl sulfate;    and-   16) mixtures thereof.

The currently preferred compounds, like 12) and 13) are moreenvironmentally-friendly materials, being rapidly biodegradablequaternary ammonium compounds that are alternatives to the traditionallyused di(long alkyl chain)dimethylammonium methyl sulfate. Suchquaternary ammonium compounds can contain long chain alk(en)yl groupsinterrupted by functional groups such as carboxy groups. Said materialsand fabric softening compositions containing them are disclosed innumerous publications such as EP-A-0,040,562, and EP-A-0,239,910.Similar quaternary ammonium compounds useful in the dryer-addedcompositions are those given hereinabove for rinse-added compositions.

Nonionic softening actives can also be used in dryer-added compositionsof the present invention. Typically, such nonionic fabric softeningmaterials have an HLB of from about 2 to about 9, more typically fromabout 3 to about 7. In general, the materials selected should berelatively crystalline, higher melting, (e.g., >25° C., preferably >40°C.) and relatively water-insoluble.

The level of nonionic softener in the solid composition, when present,is typically from about 0.1% to about 50%, preferably from about 5% toabout 30%.

Highly preferred optional nonionic softening agents for use in thepresent invention are C₁₀–C₂₆ acyl sorbitan esters and polyglycerolmonostearate. Sorbitan esters are esterified dehydration products ofsorbitol. Sorbitol, which is typically prepared by the catalytichydrogenation of glucose, can be dehydrated in well known fashion toform mixtures of 1,4- and 1,5-sorbitol anhydrides and small amounts ofisosorbides. (See U.S. Pat. No. 2,322,821, Brown, issued Jun. 29, 1943,incorporated herein by reference.) The foregoing types of complexmixtures of anhydrides of sorbitol are collectively referred to hereinas “sorbitan.” It will be recognized that this “sorbitan” mixture willalso contain some free, uncyclized sorbitol.

The preferred sorbitan ester comprises a member selected from the groupconsisting of C₁₀–C₂₆ acyl sorbitan monoesters and C₁₀–C₂₆ acyl sorbitandiesters. It is also preferred that a significant amount of trisorbitanesters are present in the ester mixture. Ester mixtures having from20–50% mono-ester, 25–50% di-ester and 10–35% of tri- and tetra-estersare preferred. For the purpose of the present invention, sorbitan esterscontaining unsaturation (e.g., sorbitan monooleate) can be utilized.

Details, including formula, of the preferred sorbitan esters can befound in U.S. Pat. No. 4,128,484, incorporated herein by reference.

Certain derivatives of the preferred sorbitan esters herein, especiallythe “lower” ethoxylates thereof, i.e., mono-, di-, and tri-esterswherein one or more of the unesterified —OH groups contain one to abouttwenty ethylene oxide units (e.g., Tweens®) are also useful in thecomposition of the present invention. Therefore, for purposes of thepresent invention, the term “sorbitan ester” includes such derivatives.

Other preferred nonionic softeners are fatty acid partial esters ofpolyhydric alcohols, or anhydrides thereof, wherein the alcohol, oranhydride, contains from about 2 to about 18, preferably from about 2 toabout 8, carbon atoms, and each fatty acid moiety contains from about 8to about 30, preferably from about 12 to about 20, carbon atoms.Typically, such softeners contain from about one to about 3, preferablyabout 2 fatty acid groups per molecule. The polyhydric alcohol portionof the ester can be ethylene glycol, glycerol, poly (e.g., di-, tri-,tetra, penta-, and/or hexa-) glycerol, xylitol, sucrose, erythritol,and/or pentaerythritol.

Dryer-added fabric care compositions employed herein can contain as asoftener component, at a level of from about 1% to about 60%, preferablyfrom about 5% to about 50%, more preferably from about 10% to about 40%,by weight of the composition of a carboxylic acid salt of a tertiaryamine and/or ester amine which has the formula:

wherein R⁵ is a long chain aliphatic group containing from about 8 toabout 30 carbon atoms; R⁶ and R⁴ are the same or different from eachother and are selected from the group consisting of aliphatic groupscontaining from about 1 to about 30, preferably 1, carbon atoms,hydroxyalkyl groups of the Formula —R⁸OH wherein R⁸ is an alkylene groupof from about 2 to about 30 carbon atoms, and alkyl ether groups of theformula R⁹(OC_(n)H_(2n))_(m)— wherein R⁹ is alkyl or alkenyl of fromabout 1 to about 30, preferably 2 or 3, carbon atoms or hydrogen, n is 2or 3, and m is from about 1 to about 30, preferably from 1 to about 5;wherein R⁴, R⁵, R⁶, R⁸, and R⁹ chains can be ester interrupted groups;and wherein R⁷ is selected from the group consisting of unsubstitutedalkyl, alkenyl, aryl, alkaryl and aralkyl of about 8 to about 30 carbonatoms, and substituted alkyl, alkenyl, aryl, alkaryl, and aralkyl offrom about 1 to about 30 carbon atoms wherein the substituents areselected from the group consisting of halogen, carboxyl, and hydroxyl.

This component provides the following benefits: superior odor, and/orimproved fabric softening performance, compared to similar compositionwhich utilize primary amine or ammonium compounds as the sole fabricconditioning agent. Either R⁴, R⁵, R⁶, R⁷, R⁸, and/or R⁹ chains cancontain unsaturation.

Examples of preferred tertiary amines as starting material for thereaction between the amine and carboxylic acid to form the tertiaryamine salts are: lauryldimethylamine, myristyldimethylamine,stearyldimethylamine, tallowdimethylamine, coconutdimethylamine,dilaurylmethylamine, distearylmethylamine, ditallowmethylamine,oleyldimethylamine, dioleylmethylamine, lauryldi(3-hydroxypropyl)amine,stearyldi(2-hydroxyethyl)amine, trilaurylamine, laurylethylmethylamine,andC₁₈H₃₇N(C₂H₄O)₁₀H.Preferred carboxylic acids are stearic, oleic, lauric, myristic,palmitic, and mixtures thereof.

The amine salt can be formed by a simple addition reaction, well knownin the art, disclosed in U.S. Pat. No. 4,237,155, Kardouche, issued Dec.2, 1980, which is incorporated herein by reference. Excessive levels offree amines can result in odor problems, and generally free aminesprovide poorer softening performance than the amine salts.

For dryer-added compositions, the actives disclosed in copendingapplication Ser. No. 08/937,536, filed Sep. 25, 1997, for DRYER-ADDEDFABRIC SOFTENER COMPOSITION USAGE TO PROVIDE COLOR AND OTHER FABRICAPPEARANCE BENEFITS by J. W. Smith, A. Corona, T. Trinh, and R. Wu areespecially suitable, said application being incorporated herein byreference. Additional fabric softening materials can be used in additionor alternatively to the above fabric softeners. These can be selectedfrom other nonionic, amphoteric and/or anionic fabric softeningmaterials. Disclosure of such materials can be found in U.S. Pat. No.4,327,133; U.S. Pat. No. 4,421,792; U.S. Pat. No. 4,426,299; U.S. Pat.No. 4,460,485; U.S. Pat. No. 3,644,203; U.S. Pat. No. 4,661,269; U.S.Pat. No. 4,439,335; U.S. Pat. No. 3,861,870; U.S. Pat. No. 4,308,151;U.S. Pat. No. 3,886,075; U.S. Pat. No. 4,233,164; U.S. Pat. No.4,401,578; U.S. Pat. No. 3,974,076; U.S. Pat. No. 4,237,016 and EP472,178, incorporated herein by reference.

Principal Solvent System

The principal solvent, when present, is typically used at an effectivelevel up to about 40% by weight, preferably from about 1% to about 25%,more preferably from about 3% to about 8%, by weight of the composition.The principal solvent can be used most effectively when in combinationwith high electrolyte level and/or the phase stabilizers, as disclosedin U.S. patent application Ser. No. 09/309,128. E.g., without the highlevel of electrolyte, the ClogP of the principal solvent systemdisclosed therein would typically be limited to a range of from about0.15 to about 0.64 as disclosed in U.S. Pat. No. 5,747,443.

With the electrolyte present, levels of principal solvent that aresubstantially less than about 15% by weight of the composition can beused, which is preferred for odor, safety and economy reasons. The phasestabilizer as defined hereinafter, in combination with a very low levelof principal solvent is sufficient to provide good clarity and/orstability of the composition when the electrolyte is present. Saidelectrolyte and/or said phase stabilizer can be used to either make acomposition translucent or clear, or can be used to increase thetemperature range at which the composition is translucent or clear.

Principal solvents are efficient in that they provide the maximumadvantage for a given weight of solvent. It is understood that“solvent”, as used herein, refers to the effect of the principal solventand not to its physical form at a given temperature, since some of theprincipal solvents are solids at ambient temperature.

Principal solvents that can be present are selected to minimize solventodor impact in the composition and to provide a low viscosity to thefinal composition.

The principal solvents are typically selected from those having a ClogPof from −2.0 to 2.6, preferably from −1.7 to 1.6, and more preferablyfrom −1.0 to 1.0.

The most preferred solvents can be identified by the appearance of thedilute treatment compositions used to treat fabrics. These dilutecompositions have dispersions of fabric softener that exhibit a moreuni-lamellar appearance than conventional fabric softener compositions.The closer to uni-lamellar the appearance, the better the compositionsseem to perform. These compositions provide surprisingly good fabricsoftening as compared to similar compositions prepared in theconventional way with the same fabric softener active.

Operable solvents have been disclosed, listed under various listings,e.g., aliphatic and/or alicyclic diols with a given number of carbonatoms; monols; derivatives of glycerine; alkoxylates of diols; andmixtures of all of the above can be found in said U.S. Pats. Nos.5,759,990 and 5,747,443 and PCT application WO 97/03169 published on 30Jan. 1997, said patents and application being incorporated herein byreference, the most pertinent disclosure appearing at pages 24–82 and94–108 (methods of preparation) of the said WO 97/03169 specificationand in columns 11–54 and 66–78 (methods of preparation) of the '443patent. Some inoperable solvents listed in the '443 disclosure can beused in mixtures with operable solvents and/or with the high electrolytelevels and/or phase stabilizers, to make concentrated fabric softenercompositions that meet the stability/clarity requirements set forthherein.

There is a clear similarity between the acceptability (formulatability)of a saturated diol and its unsaturated homologs, or analogs, havinghigher molecular weights. The unsaturated homologs/analogs have the sameformulatability as the parent saturated solvent with the condition thatthe unsaturated solvents have one additional methylene (viz., CH₂) groupfor each double bond in the chemical formula. In other words, there isan apparent “addition rule” in that for each good saturated solvent ofthis invention, which is suitable for the formulation of clear,concentrated fabric softener compositions, there are suitableunsaturated solvents where one, or more, CH₂ groups are added while, foreach CH₂ group added, two hydrogen atoms are removed from adjacentcarbon atoms in the molecule to form one carbon—carbon double bond, thusholding the number of hydrogen atoms in the molecule constant withrespect to the chemical formula of the “parent” saturated solvent. Thisis due to a surprising fact that adding a —CH₂— group to a solventchemical formula has an effect of increasing its ClogP value by about0.53, while removing two adjacent hydrogen atoms to form a double bondhas an effect of decreasing its ClogP value by about a similar amount,viz., about 0.48, thus about compensating for the —CH₂— addition.Therefore one goes from a preferred saturated solvent to the preferredhigher molecular weight unsaturated analogs/homologs containing at leastone more carbon atom by inserting one double bond for each additionalCH₂ group, and thus the total number of hydrogen atoms is kept the sameas in the parent saturated solvent, as long as the ClogP value of thenew solvent remains within the effective range. The following are someillustrative examples:

It is possible to substitute for part of the principal solvent mixture asecondary solvent, or a mixture of secondary solvents, which bythemselves are not operable as a principal solvent of this invention, aslong as an effective amount of the operable principal solvents of thisinvention is still present in the liquid concentrated, clear fabricsoftener composition. An effective amount of the principal solvents ofthis invention is at least greater than about 1%, preferably more thanabout 3%, more preferably more than about 5% of the composition, when atleast about 15% of the softener active is also present.

Principal solvents preferred for improved clarity at 50° F. are1,2-hexanediol; 1,2-pentanediol; hexylene glycol; 1,2-butanediol;1,4-cyclohexanediol; pinacol; 1,5-hexanediol; 1,6-hexanediol; and/or2,4-dimethyl-2,4-pentanediol.

Electrolyte

The clear rinse-added fabric care compositions containing a high levelof fabric softening agent of this invention can optionally, butpreferably, contain an effective amount of electrolyte, e.g., from about0.5% to about 10%, preferably from about 0.75% to about 3%, and morepreferably from about 1% to about 2%, by weight of the composition. U.S.Pat. No. 5,759,990, incorporated herein by reference, discloses that theprincipal solvent in clear formulations should have a ClogP of fromabout 0.15 to about 0.64. An effective amount of electrolyte allows theuse of principal solvents with a ClogP of from about −2.0 to about 2.6,preferably from about −1.7 to about 1.6, and more preferably from about−1.0 to about 1.0. The principal solvents are also more effective withthe high electrolyte level, thus allowing one to use less of suchprincipal solvents. Electrolyte also helps to alleviate a thickeningphenomenon some concentrate, clear fabric softener compositions arediluted.

Suitable inorganic salts for use as electrolyte include MgI₂, MgBr₂,MgCl₂, Mg(NO₃)₂, Mg₃(PO₄)₂, Mg₂P₂O₇, MgSO₄, magnesium silicate, NaI,NaBr, NaCl, NaF, Na₃(PO₄), NaSO₃, Na₂SO₄, Na₂SO₃, NaNO₃, NaIO₃,Na₃(PO₄), Na₄P₂O₇, sodium silicate, sodium metasilicate, sodiumtetrachloroaluminate, sodium tripolyphosphate (STPP), Na₂Si₃O₇, sodiumzirconate, CaF₂, CaCl₂, CaBr₂, CaI₂, CaSO₄, Ca(NO₃)₂, Ca, KI, KBr, KCl,KF, KNO₃, KIO₃, K₂SO₄, K₂SO₃, K₃(PO₄), K₄(P₂O₇), potassium pyrosulfate,potassium pyrosulfite, LiI, LiBr, LiCl, LiF, LiNO₃, AlF₃, AlCl₃, AlBr₃,AlI₃, Al₂(SO₄)₃, Al(PO₄), Al(NO₃)₃, aluminum silicate; includinghydrates of these salts and including combinations of these salts orsalts with mixed cations e.g. potassium alum AlK(SO₄)₂ and salts withmixed anions, e.g. potassium tetrachloroaluminate and sodiumtetrafluoroaluminate. Salts incorporating cations from groups IIIa, IVa,Va, VIa, VIIa, VIII, Ib, and IIb on the periodic chart with atomicnumbers >13 are also useful in reducing dilution viscosity but lesspreferred due to their tendency to change oxidation states and thus theycan adversely affect the odor or color of the formulation or lowerweight efficiency. Salts with cations from group Ia or Ia with atomicnumbers >20 as well as salts with cations from the lactinide or actinideseries are useful in reducing dilution viscosity, but less preferred dueto lower weight efficiency or toxicity. Mixtures of above salts are alsouseful.

Organic salts useful in this invention include, magnesium, sodium,lithium, potassium, zinc, and aluminum salts of the carboxylic acidsincluding formate, acetate, proprionate, pelargonate, citrate,gluconate, lactate aromatic acids e.g. benzoates, phenolate andsubstituted benzoates or phenolates, such as phenolate, salicylate,polyaromatic acids terephthalates, and polyacids e.g. oxylate, adipate,succinate, benzenedicarboxylate, benzenetricarboxylate. Other usefulorganic salts include carbonate and/or hydrogencarbonate (HCO₃ ⁻¹) whenthe pH is suitable, alkyl and aromatic sulfates and sulfonates e.g.sodium methyl sulfate, benzene sulfonates and derivatives such as xylenesulfonate, and amino acids when the pH is suitable. Electrolytes cancomprise mixed salts of the above, salts neutralized with mixed cationssuch as potassium/sodium tartrate, partially neutralized salts such assodium hydrogen tartrate or potassium hydrogen phthalate, and saltscomprising one cation with mixed anions.

Generally, inorganic electrolytes are preferred over organicelectrolytes for better weight efficiency and lower costs. Mixtures ofinorganic and organic salts can be used. Typical levels of electrolytein the compositions are less than about 10%. Preferably from about 0.5%to about 5% by weight, more preferably from about 0.75% to about 2.5%,and most preferably from about 1% to about 2% by weight of the fabricsoftener composition.

Phase Stabilizer

Phase stabilizers are highly desirable to formulating a clear ortranslucent fabric softener composition with high electrolyte levels ofthe present invention. The phase stabilizers provide an improved rangeof temperatures at which the compositions are clear and stable. Theyallow more electrolyte to be used without instability. They can alsoreduce the amount of principal solvent needed to achieve clarity and/orstability. Typical levels of the optional phase stabilizer in thesoftening compositions are from about 0.1% to about 15%, preferably fromabout 0.3% to about 7%, more preferably from about 1% to about 5% byweight of the composition.

The phase stabilizers useful in the compositions of the presentinvention are selected surface actives materials commonly comprise ofhydrophobic and hydrophilic moieties. A preferred hydrophilic moiety ispolyalkoxylated group, preferably polyethoxylated group.

Preferred phase stabilizers are nonionic surfactants derived fromsaturated and/or unsaturated primary, secondary, and/or branched, amine,amide, amine-oxide fatty alcohol, fatty acid, alkyl phenol, and/or alkylaryl carboxylic acid compounds, each preferably having from about 6 toabout 22, more preferably from about 8 to about 18, carbon atoms in ahydrophobic chain, more preferably an alkyl or alkylene chain, whereinat least one active hydrogen of said compounds is ethoxylated with ≦50,preferably ≦30, more preferably from about 5 to about 15, and even morepreferably from about 8 to about 12, ethylene oxide moieties to providean HLB of from about 8 to about 20, preferably from about 10 to about18, and more preferably from about 11 to about 15. he variousstabilizers have different advantages. For example, alkoxylated cationicmaterials or cationic surfactant complexes improve softness and provideenhanced wrinkle release benefits. In order to reduce the amount ofprincipal solvent used, the preferred phase stabilizers are alkoxylatedalkyls, alkoxylated acyl amides, alkoxylated alkyl amines or alkoxylatedquaternary alkyl ammonium salts, surfactant complexes, and mixturesthereof.

Suitable phase stabilizers also include nonionic surfactants with bulkyhead groups selected from:

-   -   a. surfactants having the formula        R¹—C(O)—Y′—[C(R⁵)]_(m)—CH₂O(R₂O)_(z)H        wherein R¹ is selected from the group consisting of saturated or        unsaturated, primary, secondary or branched chain alkyl or        alkyl-aryl hydrocarbons; said hydrocarbon chain having a length        of from about 6 to about 22; Y′ is selected from the following        groups: —O—; —N(A)—; and mixtures thereof; and A is selected        from the following groups: H; R¹; —(R²—O)_(z)—H; —(CH₂)_(x)CH₃;        phenyl, or substituted aryl, wherein 0≦x≦ about 3 and z is from        about 5 to about 30; each R² is selected from the following        groups or combinations of the following groups: —(CH₂)_(n)—        and/or —[CH(CH₃)CH₂]—; and each R⁵ is selected from the        following groups: —OH; and —O(R²O)_(z)—H; and m is from about 2        to about 4;    -   b. surfactants having the formulas:        wherein Y″=N or O; and each R⁵ is selected independently from        the following: —H, —OH, —(CH₂)xCH₃, —O(OR²)_(z)—H, —OR¹,        —OC(O)R¹, and —CH(CH₂—(OR²)_(z″)—H)—CH₂—(OR²)_(z′)—C(O)R¹, x and        R¹ are as defined above and 5≦z, z′, and z″≦20, more preferably        5≦z+z′+z″≦20, and most preferably, the heterocyclic ring is a        five member ring with Y″=O, one R⁵ is —H, two R⁵ are        —O—(R²O)z—H, and at least one R⁵ is the following structure        —CH(CH₂—(OR²)_(z″)—H)—CH₂—(OR²)_(z″)—C(O)R¹ with 8≦z+z′+z″≦20        and R¹ is a hydrocarbon with from 8 to 20 carbon atoms and no        aryl group;    -   c. polyhydroxy fatty acid amide surfactants of the formula:        R²—C(O)—N(R¹)—Z        wherein: each R¹ is H, C₁–C₄ hydrocarbyl, C₁–C₄ alkoxyalkyl, or        hydroxyalkyl; and R² is a C₅–C₃₁ hydrocarbyl moiety; and each Z        is a polyhydroxyhydrocarbyl moiety having a linear hydrocarbyl        chain with at least 3 hydroxyls directly connected to the chain,        or an ethoxylated derivative thereof; and each R′ is H or a        cyclic mono- or poly-saccharide, or alkoxylated derivative        thereof; and    -   d. mixtures thereof.

Suitable phase stabilizers also include surfactant complexes formed byone surfactant ion being neutralized with surfactant ion of oppositecharge or an electrolyte ion that is suitable for reducing dilutionviscosity and block copolymer surfactants comprising polyethylene oxidemoieties and propylene oxide moieties.

Examples of representative phase stabilizers include:

(1)—Alkyl or Alkyl-Aryl Alkoxylated Nonionic Surfactants

Suitable alkyl alkoxylated nonionic surfactants are generally derivedfrom saturated or unsaturated primary, secondary, and branched fattyalcohols, fatty acids, alkyl phenols, or alkyl aryl (e.g., benzoic)carboxylic acid, where the active hydrogen(s) is alkoxylated with ≦about 30 alkylene, preferably ethylene, oxide moieties (e.g. ethyleneoxide and/or propylene oxide). These nonionic surfactants for use hereinpreferably have from about 6 to about 22 carbon atoms on the alkyl oralkenyl chain, and are in either straight chain or branched chainconfiguration, preferably straight chain configurations having fromabout 8 to about 18 carbon atoms, with the alkylene oxide being present,preferably at the primary position, in average amounts of ≦ about 30moles of alkylene oxide per alkyl chain, more preferably from about 5 toabout 15 moles of alkylene oxide, and most preferably from about 8 toabout 12 moles of alkylene oxide. Preferred materials of this class alsohave pour points of about 70° F. and/or do not solidify in these clearformulations. Examples of alkyl alkoxylated surfactants with straightchains include Neodol® 91-8, 25-9, 1-9, 25-12, 1-9, and 45-13 fromShell, Plurafac® B-26 and C-17 from BASF, and Brij® 76 and 35 from ICISurfactants. Examples of branched alkyl alkoxylated surfactants includeTergitol® 15-S-12, 15-S-15, and 15-S-20 from Union Carbide andEmulphogene® BC-720 and BC-840 from GAF. Examples of alkyl-arylalkoxylated surfactants include Igepale® CO-620 and CO-710, from RhonePoulenc, Triton® N-111 and N-150 from Union Carbide, Dowfax® 9N5 fromDow and Lutensol® AP9 and AP14, from BASF.

(2)—Alkyl or Alkyl-Aryl Amine or Amine Oxide Nonionic AlkoxylatedSurfactants

Suitable alkyl alkoxylated nonionic surfactants with amine functionalityare generally derived from saturated or unsaturated, primary, secondary,and branched fatty alcohols, fatty acids, fatty methyl esters, alkylphenol, alkyl benzoates, and alkyl benzoic acids that are converted toamines, amine-oxides, and optionally substituted with a second alkyl oralkyl-aryl hydrocarbon with one or two alkylene oxide chains attached atthe amine functionality each having ≦ about 50 moles alkylene oxidemoieties (e.g. ethylene oxide and/or propylene oxide) per mole of amine.The amine, amide or amine-oxide surfactants for use herein have fromabout 6 to about 22 carbon atoms, and are in either straight chain orbranched chain configuration, preferably there is one hydrocarbon in astraight chain configuration having about 8 to about 18 carbon atomswith one or two alkylene oxide chains attached to the amine moiety, inaverage amounts of ≦50 about moles of alkylene oxide per amine moiety,more preferably from about 5 to about 15 moles of alkylene oxide, andmost preferably a single alkylene oxide chain on the amine moietycontaining from about 8 to about 12 moles of alkylene oxide per aminemoiety. Preferred materials of this class also have pour points about70° F. and/or do not solidify in these clear formulations. Examples ofethoxylated amine surfactants include Berol® 397 and 303 from RhonePoulenc and Ethomeens® C/20, C25, T/25, S/20, S/25 and Ethodumeens® T/20and T25 from Akzo.

Preferably, the compounds of the alkyl or alkyl-aryl alkoxylatedsurfactants and alkyl or alkyl-aryl amine, amide, and amine-oxidealkoxylated have the following general formula:R¹ _(m)—Y—[(R²—O)_(z)—H]_(p)

-   -   wherein each R¹ is selected from the group consisting of        saturated or unsaturated, primary, secondary or branched chain        alkyl or alkyl-aryl hydrocarbons; said hydrocarbon chain        preferably having a length of from about 6 to about 22, more        preferably from about 8 to about 18 carbon atoms, and even more        preferably from about 8 to about 15 carbon atoms, preferably,        linear and with no aryl moiety; wherein each R² is selected from        the following groups or combinations of the following groups:        —(CH₂)_(n)— and/or —[CH(CH₃)CH₂]—; wherein about 1<n≦ about 3; Y        is selected from the following groups: —O—; —N(A)_(q)—; —C(O)O—;        —(O←)N(A)_(q)—; —B—R³—O—; —B—R³—N(A)_(q)—; —B—R³—C(O)O—;        —B—R³—N(→O)(A)—; and mixtures thereof; wherein A is selected        from the following groups: H; R¹; —(R²—O)_(z)—H; —(CH₂)_(x)CH₃;        phenyl, or substituted aryl, wherein 0≦x≦ about 3 and B is        selected from the following groups: —O—; —N(A)—; —C(O)O—; and        mixtures thereof in which A is as defined above; and wherein        each R³ is selected from the following groups: R²; phenyl; or        substituted aryl. The terminal hydrogen in each alkoxy chain can        be replaced by a short chain C₁₋₄ alkyl or acyl group to “cap”        the alkoxy chain. z is from about 5 to about 30. p is the number        of ethoxylate chains, typically one or two, preferably one and m        is the number of hydrophobic chains, typically one or two,        preferably one and q is a number that completes the structure,        usually one.

Preferred structures are those in which m=1, p=1 or 2, and 5≦z≦30, and qcan be 1 or 0, but when p=2, q must be 0; more preferred are structuresin which m=1, p=1 or 2, and 7≦z≦20; and even more preferred arestructures in which m=1, p=1 or 2, and 9≦z≦12. The preferred y is 0.

(3)—Alkoxylated and Non-Alkoxylated Nonionic Surfactants with Bulky HeadGroups

Suitable alkoxylated and non-alkoxylated phase stabilizers with bulkyhead groups are generally derived from saturated or unsaturated,primary, secondary, and branched fatty alcohols, fatty acids, alkylphenol, and alkyl benzoic acids that are derivatized with a carbohydrategroup or heterocyclic head group. This structure can then be optionallysubstituted with more alkyl or alkyl-aryl alkoxylated or non-alkoxylatedhydrocarbons. The heterocyclic or carbohydrate is alkoxylated with oneor more alkylene oxide chains (e.g. ethylene oxide and/or propyleneoxide) each having ≦about 50, preferably ≦ about 30, moles per mole ofheterocyclic or carbohydrate. The hydrocarbon groups on the carbohydrateor heterocyclic surfactant for use herein have from about 6 to about 22carbon atoms, and are in either straight chain or branched chainconfiguration, preferably there is one hydrocarbon having from about 8to about 18 carbon atoms with one or two alkylene oxide chainscarbohydrate or heterocyclic moiety with each alkylene oxide chainpresent in average amounts of ≦ about 50, preferably ≦about 30, moles ofcarbohydrate or heterocyclic moiety, more preferably from about 5 toabout 15 moles of alkylene oxide per alkylene oxide chain, and mostpreferably between about 8 and about 12 moles of alkylene oxide totalper surfactant molecule including alkylene oxide on both the hydrocarbonchain and on the heterocyclic or carbohydrate moiety. Examples of phasestabilizers in this class are Tween® 40, 60, and 80 available from ICISurfactants.

Preferably the compounds of the alkoxylated and non-alkoxylated nonionicsurfactants with bulky head groups have the following general formulas:R¹—C(O)—Y′—[C(R⁵)]_(m)—CH₂O(R₂O)_(z)Hwherein R¹ is selected from the group consisting of saturated orunsaturated, primary, secondary or branched chain alkyl or alkyl-arylhydrocarbons; said hydrocarbon chain having a length of from about 6 toabout 22; Y′ is selected from the following groups: —O—; —N(A)—; andmixtures thereof; and A is selected from the following groups: H; R¹;—(R²—O)_(z)—H; —(CH₂)_(x)CH₃; phenyl, or substituted aryl, wherein 0≦x≦about 3 and z is from about 5 to about 30; each R is selected from thefollowing groups or combinations of the following groups: —(CH₂)_(n)—and/or —[CH(CH₃)CH₂]—; and each R⁵ is selected from the followinggroups: —OH; and —O(R²O)_(z)—H; and m is from about 2 to about 4;

Another useful general formula for this class of surfactants is

-   -   wherein Y″=N or O; and each R⁵ is selected independently from        the following: —H, —OH, —(CH₂)_(x)CH₃, —(OR²)_(z)—H, —OR¹,        —OC(O)R¹, and —CH₂(CH₂—(OR²)_(z″)—H)—CH₂—(OR²)_(z′)—C(O)R¹. With        x R¹, and R² as defined above in section D above and z, z′, and        z″ are all from about 5≦ to ≦ about 20, more preferably the        total number of z+z′+z″ is from about 5≦ to ≦ about 20. In a        particularly preferred form of this structure the heterocyclic        ring is a five member ring with Y″=O, one R⁵ is —H, two R⁵ are        —O—(R²O)_(z)—H, and at least one R⁵ has the following structure        —CH(CH₂—(OR²)_(z″)—H)—CH₂—(OR²)_(z′)—OC(O) R¹ with the total        z+z′+z″=to from about 8≦ to ≦ about 20 and R¹ is a hydrocarbon        with from about 8 to about 20 carbon atoms and no aryl group.

Another group of surfactants that can be used are polyhydroxy fatty acidamide surfactants of the formula:R⁶—C(O)—N(R⁷)—Wwherein: each R⁷ is H, C₁–C₄ hydrocarbyl, C₁–C₄ alkoxyalkyl, orhydroxyalkyl, e.g., 2-hydroxyethyl, 2-hydroxypropyl, etc., preferablyC₁–C₄ alkyl, more preferably C₁ or C₂ alkyl, most preferably C₁ alkyl(i.e., methyl) or methoxyalkyl; and R⁶ is a C₅–C₃₁ hydrocarbyl moiety,preferably straight chain C₇–C₁₉ alkyl or alkenyl, more preferablystraight chain C₉–C₁₇ alkyl or alkenyl, most preferably straight chainC₁₁–C₁₇ alkyl or alkenyl, or mixture thereof; and W is apolyhydroxyhydrocarbyl moiety having a linear hydrocarbyl chain with atleast 3 hydroxyls directly connected to the chain, or an alkoxylatedderivative (preferably ethoxylated or propoxylated) thereof W preferablywill be derived from a reducing sugar in a reductive amination reaction;more preferably W is a glycityl moiety. W preferably will be selectedfrom the group consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n)—CH₂OH, —CH₂ —(CHOH)₂(CHOR′)(CHOH)—CH₂OH, where nis an integer from 3 to 5, inclusive, and R′ is H or a cyclic mono- orpoly-saccharide, and alkoxylated derivatives thereof. Most preferred areglycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂O. Mixtures ofthe above W moieties are desirable.

R⁶ can be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl,N-butyl, N-isobutyl, N-2-hydroxyethyl, N−1-methoxypropyl, orN-2-hydroxypropyl.

R⁶—CO—N< can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc.

W can be 1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl,1-deoxylactityl, 1-deoxygalactityl, 1-deoxymannityl,1-deoxymaltotriotityl, etc.

(4)—Alkoxylated Cationic Quaternary Ammonium Surfactants

Alkoxylated cationic quaternary ammonium surfactants suitable for thisinvention are generally derived from fatty alcohols, fatty acids, fattymethyl esters, alkyl substituted phenols, alkyl substituted benzoicacids, and/or alkyl substituted benzoate esters, and/or fatty acids thatare converted to amines which can optionally be further reacted withanother long chain alkyl or alkyl-aryl group; this amine compound isthen alkoxylated with one or two alkylene oxide chains each having ≦about 50 moles alkylene oxide moieties (e.g. ethylene oxide and/orpropylene oxide) per mole of amine. Typical of this class are productsobtained from the quaternization of aliphatic saturated or unsaturated,primary, secondary, or branched amines having one or two hydrocarbonchains from about 6 to about 22 carbon atoms alkoxylated with one or twoalkylene oxide chains on the amine atom each having less than ≦ about 50alkylene oxide moieties. The amine hydrocarbons for use herein have fromabout 6 to about 22 carbon atoms, and are in either straight chain orbranched chain configuration, preferably there is one alkyl hydrocarbongroup in a straight chain configuration having about 8 to about 18carbon atoms. Suitable quaternary ammonium surfactants are made with oneor two alkylene oxide chains attached to the amine moiety, in averageamounts of ≦ about 50 moles of alkylene oxide per alkyl chain, morepreferably from about 3 to about 20 moles of alkylene oxide, and mostpreferably from about 5 to about 12 moles of alkylene oxide perhydrophobic, e.g., alkyl group. Preferred materials of this class alsohave a pour points below about 70° F. and/or do not solidify in theseclear formulations. Examples of suitable phase stabilizers of this typeinclude Ethoquad® 18/25, C/25, and O/25 from Akzo and Variquat®-66 (softtallow alkyl bis(polyoxyethyl) ammonium ethyl sulfate with a total ofabout 16 ethoxy units) from Witco.

Preferably, the compounds of the ammonium alkoxylated cationicsurfactants have the following general formula:{R¹ _(m—Y—[(R) ²—O)_(z)—H]_(p)}⁺X⁻

-   -   wherein R¹ and R² are as defined previously in section D above;    -   Y is selected from the following groups: =N⁺—(A)_(q);        —(CH₂)_(n)—N⁺—(A)_(q); —B—(CH₂)_(n)—N⁺—(A)₂;        -(phenyl)-N⁺—(A)_(q); —(B-phenyl)-N⁺—(A)_(q); with n being from        about 1 to about 4.

Each A is independently selected from the following groups: H; R¹;—(R²O)_(z)—H; —(CH₂)_(x)CH₃; phenyl, and substituted aryl; where 0≦x≦about 3; and B is selected from the following groups: —O—; —NA—; —NA₂;—C(O)O—; and —C(O)N(A)—; wherein R² is defined as hereinbefore; q=1 or2; and

X⁻ is an anion which is compatible with fabric softener actives andadjunct ingredients.

Preferred structures are those in which m=1, p=1 or 2, and about 5≦z≦about 50, more preferred are structures in which m=1, p=or 2, and about7≦z≦ about 20, and most preferred are structures in which m=1, p=1 or 2,and about 9≦z≦ about 12.

(5)—Surfactant Complexes

Surfactant complexes are considered to be surfactant ions neutralizedwith a surfactant ion of opposite charge or a surfactant neutralizedwith an electrolyte that is suitable for reducing dilution viscosity, anammonium salt, or a polycationic ammonium salt. For the purpose of thisinvention, if a surfactant complex is formed by surfactants of oppositecharge, it is preferable that the surfactants have distinctly differentchain lengths e.g. a long-chain surfactant complexed with a short-chainsurfactant to enhance the solubility of the complex and it is morepreferable that the that the long chain surfactant be the amine orammonium containing surfactant. Long chain surfactants are defined ascontaining alkyl chains with from about 6 to about 22 carbon atoms.These alkyl chains can optionally contain a phenyl or substituted phenylgroup or alkylene oxide moieties between the chain and the head group.Short chain surfactants are defined as containing alkyl chains with lessthan 6 carbons and optionally these alkyl chains could contain a phenylor substituted phenyl group or alkylene oxide moieties between the alkylchain and the head group. Examples of suitable surfactant complexesinclude mixtures of Armeen® APA-10 and calcium xylene sulfonate, ArmeenAPA-10 and magnesium chloride, lauryl carboxylate and triethanol amine,linear alkyl benzene sulfonate and C₅-dimethyl amine, or alkylethoxylated sulfate and tetrakis N,N,N′N′ (2-hydroxylpropyl)ethylenediamine.

Preferably, long-chain surfactants for making complexes have thefollowing general formula:R¹—Y²wherein R¹ is as hereinbefore from section D above and Y² can be chosenfrom the following structures: —N(A)₂; —C(O)N(A)₂; —(O←)N(A)₂;—B—R³—N(A)₂; —B—R³—C(O)N(A)₂; —B—R³—N(→O)(A)₂; —CO₂ ⁻; —SO₃ ⁻²; —OSO₃⁻²; —O(R²O)_(x)CO₂; —O(R²O)_(x)SO₃ ⁻²; and —O(R²O)_(x)OSO₃ ⁻²; with Band R³ as is hereinbefore section D above and 0≦x≦4.

Preferably, short-chain surfactants for making complexes have thefollowing general formula:R⁴—Y²wherein R¹, R³, B, and Y² are as hereinbefore and R⁴ can be chosen fromthe following: —(CH₂)_(y)CH₃; —(CH₂)_(y)-phenyl or—(CH₂)_(y)-substituted phenyl with 0≦y≦6.(6)—Block Copolymers Obtained by Copolymerization of Ethylene Oxide andPropylene Oxide

Suitable polymers include a copolymer having blocks of terephthalate andpolyethylene oxide. More specifically, these polymers are comprised ofrepeating units of ethylene and/or propylene terephthalate andpolyethylene oxide terephthalate at a preferred molar ratio of ethyleneterephthalate units to polyethylene oxide terephthalate units of fromabout 25:75 to about 35:65, said polyethylene oxide terephthalatecontaining polyethylene oxide blocks having molecular weights of fromabout 300 to about 2000. The molecular weight of this polymer is in therange of from about 5,000 to about 55,000.

Another preferred polymer is a crystallizable polyester with repeatunits of ethylene terephthalate units containing from about 10% to about15% by weight of ethylene terephthalate units together with from about10% to about 50% by weight of polyoxyethylene terephthalate units,derived from a polyoxyethylene glycol of average molecular weight offrom about 300 to about 6,000, and the molar ratio of ethyleneterephthalate units to polyoxyethylene terephthalate units in thecrystallizable polymeric compound is between 2:1 and 6:1. Examples ofthis polymer include the commercially available materials Zelcon® 4780(from DuPont) and Milease® T (from ICI).

Highly preferred polymers have the generic formula:X—(OCH₂CH₂)_(n)—[O—C(O)—R¹—C(O)—O—R²)_(u)—[O—C(O)—R¹—C(O)—O)—(CH₂CH₂O)_(n)—X  (1)in which X can be any suitable capping group, with each X being selectedfrom the group consisting of H, and alkyl or acyl groups containing fromabout 1 to about 4 carbon atoms, preferably methyl, n is selected forwater solubility and generally is from about 6 to about 113, preferablyfrom about 20 to about 50, and u is critical to formulation in a liquidcomposition having a relatively high ionic strength. There should bevery little material in which u is greater than 10. Furthermore, thereshould be at least 20%, preferably at least 40%, of material in which uranges from about 3 to about 5.

The R¹ moieties are essentially 1,4-phenylene moieties. As used herein,the term “the R¹ moieties are essentially 1,4-phenylene moieties” refersto compounds where the R¹ moieties consist entirely of 1,4-phenylenemoieties, or are partially substituted with other arylene or alkarylenemoieties, alkylene moieties, alkenylene moieties, or mixtures thereof.Arylene and alkarylene moieties which can be partially substituted for1,4-phenylene include 1,3-phenylene, 1,2-phenylene, 1,8-naphthylene,1,4-naphthylene, 2,2-biphenylene, 4,4-biphenylene and mixtures thereof.Alkylene and alkenylene moieties which can be partially substitutedinclude ethylene, 1,2-propylene, 1,4-butylene, 1,5-pentylene,1,6-hexamethylene, 1,7-heptamethylene, 1,8-octamethylene,1,4-cyclohexylene, and mixtures thereof.

For the R¹ moieties, the degree of partial substitution with moietiesother than 1,4-phenylene should be such that the desired properties ofthe compound are not adversely affected to any great extent. Generally,the degree of partial substitution which can be tolerated will dependupon the backbone length of the compound, i.e., longer backbones canhave greater partial substitution for 1,4-phenylene moieties. Usually,compounds where the R¹ comprise from about 50% to about 100%1,4-phenylene moieties (from 0 to about 50% moieties other than1,4-phenylene) are adequate. Preferably, the R¹ moieties consistentirely of (i.e., comprise 100%) 1,4-phenylene moieties, i.e., each R¹moiety is 1,4-phenylene.

For the R² moieties, suitable ethylene or substituted ethylene moietiesinclude ethylene, 1,2-propylene, 1,2-butylene, 1,2-hexylene,3-methoxy-1,2-propylene and mixtures thereof. Preferably, the R²moieties are essentially ethylene moieties, 1,2-propylene moieties ormixture thereof. Surprisingly, inclusion of a greater percentage of1,2-propylene moieties tends to improve the water solubility of thecompounds.

Therefore, the use of 1,2-propylene moieties or a similar branchedequivalent is desirable for incorporation of any substantial part of thepolymer in the liquid fabric softener compositions. Preferably, fromabout 75% to about 100%, more preferably from about 90% to about 100%,of the R² moieties are 1,2-propylene moieties.

The value for each n is at least about 6, and preferably is at leastabout 10. The value for each n usually ranges from about 12 to about113. Typically, the value for each n is in the range of from about 12 toabout 43.

A more complete disclosure of these polymers is contained in EuropeanPatent Application 185,427, Gosselink, published Jun. 25, 1986,incorporated herein by reference.

Other preferred copolymers include surfactants, such as thepolyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) reverseblock polymers.

The copolymer can optionally contain propylene oxide in an amount up toabout 15% by weight. Other preferred copolymer surfactants can beprepared by the processes described in U.S. Pat. No. 4,223,163, issuedSep. 16, 1980, Builloty, incorporated herein by reference.

Suitable block polyoxyethylene-polyoxypropylene polymeric compounds thatmeet the requirements described hereinbefore include those based onethylene glycol, propylene glycol, glycerol, trimethylolpropane andethylenediamine as initiator reactive hydrogen compound. Certain of theblock polymer surfactant compounds designated PLURONIC® and TETRONIC® bythe BASF-Wyandotte Corp., Wyandotte, Mich., are suitable in compositionsof the invention.

A particularly preferred copolymer contains from about 40% to about 70%of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymerblend comprising about 75%, by weight of the blend, of a reverse blockcopolymer of polyoxyethylene and polyoxypropylene containing 17 moles ofethylene oxide and 44 moles of propylene oxide; and about 25%, by weightof the blend, of a block copolymer of polyoxyethylene andpolyoxypropylene initiated with trimethylolpropane and containing 99moles of propylene oxide and 24 moles of ethylene oxide per mole oftrimethylolpropane.

Suitable for use as copolymer are those having relatively highhydrophilic-lipophilic balance (HLB).

Other polymers useful herein include the polyethylene glycols having amolecular weight of from about 950 to about 30,000 which can be obtainedfrom the Dow Chemical Company of Midland, Mich. Such compounds forexample, have a melting point within the range of from about 30° C. toabout 100° C., can be obtained at molecular weights of 1,450, 3,400,4,500, 6,000, 7,400, 9,500, and 20,000. Such compounds are formed by thepolymerization of ethylene glycol with the requisite number of moles ofethylene oxide to provide the desired molecular weight and melting pointof the respective polyethylene glycol.

(7)—Alkyl Amide Alkoxylated Nonionic Surfactants

Suitable surfactants have the formula:R—C(O)—N(R⁴)_(n)—[(R¹O)_(x)(R²O)_(y)R³]_(m)wherein R is C₇₋₂₁ linear alkyl, C₇₋₂₁ branched alkyl, C₇₋₂₁ linearalkenyl, C₇₋₂₁ branched alkenyl, and mixtures thereof. Preferably R isC₈₋₁₈ linear alkyl or alkenyl.

R¹ is —CH₂—CH2—, R₂ is C₃–C₄ linear alkyl, C₃–C₄ branched alkyl, andmixtures thereof; preferably R² is —CH(CH₃)—CH₂—. Surfactants whichcomprise a mixture of R1 and R2 units preferably comprise from about 4to about 12 —CH₂—CH₂— units in combination with from about 1 to about 4—CH(CH₃)—CH₂— units. The units may be alternating or grouped together inany combination suitable to the formulator. Preferably the ratio of R¹units to R² units is from about 4:1 to about 8:1. Preferably an R² unit(i.e. —C(CH₃)H—CH₂—) is attached to the nitrogen atom followed by thebalance of the chain comprising from about 4 to 8 —CH₂—CH₂— units.

R³ is hydrogen, C₁–C₄ linear alkyl, C₃–C₄ branched alkyl, and mixturesthereof; preferably hydrogen or methyl, more preferably hydrogen.

R⁴ is hydrogen, C₁–C₄ linear alkyl, C₃–C₄ branched alkyl, and mixturesthereof; preferably hydrogen. When the index m is equal to 2 the index nmust be equal to 0 and the R4 unit is absent.

The index m is 1 or 2, the index n is 0 or 1, provided that m+n equals2; preferably m is equal to 1 and n is equal to 1, resulting in one—[(R¹O)_(x)(R²O)_(y)R³] unit and R4 being present on the nitrogen. Theindex x is from 0 to about 50, preferably from about 3 to about 25, morepreferably from about 3 to about 10. The index y is from 0 to about 10,preferably 0, however when the index y is not equal to 0, y is from 1 toabout 4. Preferably all the alkyleneoxy units are ethyleneoxy units.

Examples of suitable ethoxylated alkyl amide surfactants are Rewopal® C₆from Witco, Amidox® C5 from Stepan, and Ethomid® O/17 and Ethomid® HT/60from Akzo.; and

(8)—Mixtures Thereof.

Auxiliary Whiteness Preservatives

Auxiliary whiteness preservatives are optionally, but preferablyincorporated in order to improve fabric whiteness. Auxiliary whitenesspreservatives can be used together with the metal chelant to give anextra boost to whiteness maintenance.

1. Brighteners

Optical brighteners also known as fluorescent whitening agents (FWAs) orfluorescent brighteners preserve whiteness by compensating for theyellow appearance by adding a complementary color to the fabric and thusthe undesired yellowing is rendered invisible. When a white fabric isstored for a length of time, it can appear to be yellow. Not to be boundby theory, but it is believed that auto-oxidation of polyunsaturatedmaterials such as body fatty acids or fabric softener actives generatecompounds that appear yellow on white fabrics, because these compoundsabsorb short-wavelength light, light in the range of violet to blue orwavelengths between about 370 nm to 550 nm. Optical brighteners absorblight in the range of ultraviolet light and emit light via fluorescencein the blue to blue violet range of the spectrum. Thus opticalbrighteners replace this missing part of the spectrum on yellowingfabric and so a white appearance is retained.

The product contains from about 0.005% to about 5%, preferably fromabout 0.05% to about 3%, more preferably from about 0.1% to about 2%,even more preferably from about 0.15% to about 1%, by weight of thecomposition, optical brightener. Lower levels of brightener are used inthe presence of the metal chelating compound. In the absence of themetal chelating compound, higher levels of brightener are preferred.

Preferred optical brighteners are colorless on the substrate and do notabsorb in the visible part of the spectrum. Preferred opticalbrighteners are also lightfast, meaning that these do not degradesubstantially in sunlight. Optical brighteners suitable for use in thisinvention absorb light in the ultraviolet portion of the spectrumbetween 275 nm and about 400 nm and emit light in the violet toviolet-blue range of the spectrum from about 400 nm to about 550 nm.Preferably, the optical brightener will contain an uninterrupted chainof conjugated double bounds. Optical brighteners are typically, but notlimited to, derivatives of stilbene or 4,4′-diaminostilbene, biphenyl,five-membered heterocycles such as triazoles, oxazoles, imidiazoles,etc., or six-membered heterocycles (coumarins, naphthalamide,s-triazine, etc.). Many specific brightener structures are described inThe Kirk-Othmer Encyclopedia of Chemistry 3^(rd) Ed., pp 214–226 and inreferences therein U.S. Pat. No. 5,759,990 at column 21, lines 15–60;said references being incorporated herein by reference as suitable foruse in this invention. Ionic brighteners with a positive or negativecharge are preferred as this improves solubility in the compositionsdisclosed herein and thus are easier to formulate and are more stable.Cationic brighteners are also preferred since these can competeeffectively with cationic fabric softeners to partition to the surfaceof the fabric.

Some preferred, but nonlimiting brighteners are Optiblanc® GL andOptiblanc® LSN from 3V Inc., Weehawken, N.J., Tinopals® CBS SP Slurry33, PLC, UNPA-GX, 4BM, 4BMS, 5BM, 5BMS, 5BM-GX, AMS-GX, DMS-X, DCSLiquid, K, ERN, LCS, LFW, and TAS, Univex®, SK, ERN, and AT, from Ciba,High Point, N.C., Blankophor® FBW, FB, LPG, and HRS, from Mobay. Inaddition to preventing auto-oxidation, some brighteners also prevent dyetransfer.

2. Bluing Agents

Bluing agents also act to preserve whiteness by compensating for theyellow appearance by again adding a complementary color to the fabricand thus the undesired yellowing is no longer noticeable. Like opticalbrighteners, bluing agents replace this missing part of the spectrum andso a white appearance is retained.

3. UV Absorbers

Not to be bound by theory, but UV absorbers can operate by protectingthe fabric and any fabric softener compound deposited on the fabric fromUV exposure. UV light is know to initiate auto-oxidation processes andUV absorbers can be deposited on fabric in such a way that UV light isblocked from the fabric and unsaturated fatty materials, thus preventingthe initiation of auto-oxidation.

5. Oxidative Stabilizers

Oxidative stabilizers can be present in the compositions of the presentinvention and these prevent yellowing by acting as a scavenger for theoxidative processes, thus preventing and/or terminating auto-oxidation,or by reversing oxidation and thus reversing yellowing. The term“oxidative stabilizer,” as used herein, includes antioxidants andreductive agents. These agents are present at a level of from 0% toabout 2%, preferably from about 0.01% to about 0.2%, more preferablyfrom about 0.035% to about 0.1% for antioxidants, and, preferably, fromabout 0.01% to about 0.2% for reductive agents.

Examples of antioxidants that can be added to the compositions and inthe processing of this invention include a mixture of ascorbic acid,ascorbic palmitate, propyl gallate, available from Eastman ChemicalProducts, Inc., under the trade names Tenox® PG and Tenox® S-1; amixture of BHT (butylated hydroxytoluene), BHA (butylatedhydroxyanisole), propyl gallate, and citric acid, available from EastmanChemical Products, Inc., under the trade name Tenox®-6; butylatedhydroxytoluene, available from UOP Process Division under the trade nameSustane® BHT; tertiary butylhydroquinone, Eastman Chemical Products,Inc., as Tenox® TBHQ; natural tocopherols, Eastman Chemical Products,Inc., as Tenox® GT-1/GT-2; and butylated hydroxyanisole, EastmanChemical Products, Inc., as BHA; long chain esters (C₈–C₂₂) of gallicacid, e.g., dodecyl gallate; Irganox® 1010; Irganox® 1035; Irganox® B1171; Irganox® 1425; Irganox® 3114; Irganox® 3125; and mixtures thereof;preferably Irganox® 3125, Irganox® 1425, Irganox® 3114, and mixturesthereof; more preferably Irganox® 3125 alone or mixed with citric acidand/or other chelators such as isopropyl citrate, Dequest® 2010,available from Monsanto with a chemical name of1-hydroxyethylidene-1,1-diphosphonic acid (etidronic acid), and Tiron®,available from Kodak with a chemical name of4,5-dihydroxy-m-benzene-sulfonic acid/sodium salt, and DTPA®, availablefrom Aldrich with a chemical name of diethylenetriaminepentaacetic acid.

Oxidative stabilizers can also be added at any point during the processof making fabric softener raw materials where polyunsaturated compoundswould be present. E.g., these could be added into oils used to makefatty acids, during fatty acid making and/or storage during fabricsoftener making and/or storage. These assure good odor stability underlong term storage conditions.

Other Optional Ingredients

The fabric care composition of the present invention can optionallycontain adjunct odor-controlling materials, chelating agents, antistaticagents, insect and moth repelling agents, colorants, especially bluingagents, antioxidants, and mixtures thereof in addition to the cyclicsilicone molecules. The total level of optional ingredients is low,preferably less than about 5%, more preferably less than about 3%, andeven more preferably less than about 2%, by weight of the usagecomposition. These optional ingredients exclude the other ingredientsspecifically mentioned hereinbefore. Incorporating adjunctodor-controlling materials can enhance the capacity of the cyclodextrinto control odors as well as broaden the range of odor types and moleculesizes which can be controlled. Such materials include, for example,metallic salts, water-soluble cationic and anionic polymers, zeolites,water-soluble bicarbonate salts, and mixtures thereof.

Water-Soluble Polyionic Polymers

Some water-soluble polyionic polymers, e.g., water-soluble cationicpolymer and water-soluble anionic polymers can be used in thecomposition of the present invention to provide additional odor controlbenefits.

Cationic Polymers, e.g., Polyamines

Water-soluble cationic polymers, e.g., those containing aminofunctionalities, amido functionalities, and mixtures thereof, are usefulin the present invention to control certain acid-type odors.

Anionic Polymers, e.g., Polyacrylic Acid

Water-soluble anionic polymers, e.g., polyacrylic acids and theirwater-soluble salts are useful in the present invention to controlcertain amine-type odors. Preferred polyacrylic acids and their alkalimetal salts have an average molecular weight of less than about 20,000,more preferably less than 5,000000, preferably less than 10,000, morepreferably from about 500 to about 5,000. Polymers containing sulfonicacid groups, phosphoric acid groups, phosphonic acid groups, and theirwater-soluble salts, and mixtures thereof, and mixtures with carboxylicacid and carboxylate groups, are also suitable.

Water-soluble polymers containing both cationic and anionicfunctionalities are also suitable. Examples of these polymers are givenin U.S. Pat. No. 4,909,986, issued Mar. 20, 1990 to N. Kobayashi and A.Kawazoe, incorporated herein by reference. Another example ofwater-soluble polymers containing both cationic and anionicfunctionalities is a copolymer of dimethyldiallyl ammonium chloride andacrylic acid, commercially available under the trade name Merquat 280®from Calgon.

When a water-soluble polymer is used it is typically present at a levelof from about 0.001% to about 3%, preferably from about 0.005% to about2%, more preferably from about 0.01% to about 1%, and even morepreferably from about 0.05% to about 0.5%, by weight of the usagecomposition.

Antistatic Agents

The composition of the present invention can optionally contain aneffective amount of antistatic agent to provide the treated clothes within-wear static. Preferred antistatic agents are those that are watersoluble in at least an effective amount, such that the compositionremains a clear solution. Examples of these antistatic agents aremonoalkyl cationic quaternary ammonium compounds, e.g., mono(C₁₀—C₁₄alkyl)trimethyl ammonium halide, such as monolauryl trimethyl ammoniumchloride, hydroxycetyl hydroxyethyl dimethyl ammonium chloride,available under the trade name Dehyquart E® from Henkel, and ethylbis(polyethoxy ethanol) alkylammonium ethylsulfate, available under thetrade name Variquat 66® from Witco Corp., polyethylene glycols,polymeric quaternary ammonium salts, such as polymers conforming to thegeneral formula:—[N(CH₃)₂—(CH₂)₃—NH—CO—NH—(CH₂)₃—N(CH₃)₂ ⁺—CH₂CH₂OCH₂CH₂]—_(x) ²⁺2x[Cl⁻]available under the trade name Mirapol A-15® from Rhône-Poulenc, and—[N(CH₃)₂—(CH₂)₃—NH—CO—(CH₂)₄—CO—NH—(CH₂)₃—N(CH₃)₂—(CH₂CH₂OCH₂CH₂]—_(x)⁺x[Cl^(−],)available under the trade name Mirapol AD-1® from Rhône-Poulenc,quaternized polyethyleneimines,vinylpyrrolidone/methacrylamidopropyltrimethylammonium chloridecopolymer, available under the trade name Gafquat HS-100® from GAF;triethonium hydrolyzed collagen ethosulfate, available under the tradename Quat-Pro E® from Maybrook; neutralized sulfonated polystyrene,available, e.g., under the trade name Versa TL-130® from Alco Chemical,neutralized sulfonated styrene/maleic anhydride copolymers, available,e.g., under the trade name Versa TL-4® from Alco Chemical; and mixturesthereof.

It is preferred that a no foaming, or low foaming, agent is used, toavoid foam formation during fabric treatment. It is also preferred thatpolyethoxylated agents such as polyethylene glycol or Variquat 66® arenot used when alpha-cyclodextrin is used. The polyethoxylate groups havea strong affinity to, and readily complex with, alpha-cyclodextrin whichin turn depletes the uncomplexed cyclodextrin available for odorcontrol.

When an antistatic agent is used it is typically present at a level offrom about 0.05% to about 10%, preferably from about 0.1% to about 5%,more preferably from about 0.3% to about 3%, by weight of the usagecomposition.

Insect and/or Moth Repelling Agent

The composition of the present invention can optionally contain aneffective amount of insect and/or moth repelling agents. Typical insectand moth repelling agents are pheromones, such as anti-aggregationpheromones, and other natural and/or synthetic ingredients. Preferredinsect and moth repellent agents useful in the composition of thepresent invention are perfume ingredients, such as citronellol,citronellal, citral, linalool, cedar extract, geranium oil, sandalwoodoil, 2-(diethylphenoxy)ethanol, 1-dodecene, etc. Other examples ofinsect and/or moth repellents useful in the composition of the presentinvention are disclosed in U.S. Pat. Nos. 4,449,987, 4,693,890,4,696,676, 4,933,371, 5,030,660, 5,196,200, and in “Semio Activity ofFlavor and Fragrance Molecules on Various Insect Species”, B. D.Mookherjee et al., published in Bioactive Volatile Compounds fromPlants, ASC Symposium Series 525, R. Teranishi, R. G. Buttery, and H.Sugisawa, 1993, pp. 35–48, all of said patents and publications beingincorporated herein by reference. When an insect and/or moth repellentis used it is typically present at a level of from about 0.005% to about3%, by weight of the usage composition.

Colorant

Colorants and dyes, especially bluing agents, can be optionally added tothe fabric care compositions for visual appeal and performanceimpression. When colorants are used, they are used at extremely lowlevels to avoid fabric staining. Preferred colorants for use in thepresent compositions are highly water-soluble dyes, e.g., Liquitint®dyes available from Milliken Chemical Co. Non-limiting examples ofsuitable dyes are, Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, Liquitint Green HMC®, Liquitint Yellow II®, and mixturesthereof, preferably Liquitint Blue HP®, Liquitint Blue 65®, LiquitintPatent Blue®, Liquitint Royal Blue®, Liquitint Experimental Yellow8949-43®, and mixtures thereof.

Optional Anti-Clogging Agent

Optional anti-clogging agent which enhances the wetting andanti-clogging properties of the composition, especially when starch ispresent, is chosen from the group of polymeric glycols of alkanes andolefins having from 2 to about 6, preferably 2 carbon atoms. Theanti-clogging agent inhibits the formation of “plugs” in the spraynozzle. An example of the preferred anti-clogging agent is polyethyleneglycol having an average molecular weight of from about 800 to about12,000, more preferably from about 1,400 to about 8,000. When used, theanti-clogging agent is present at a level of from about 0.01% to about1%, preferably from about 0.05% to about 0.5%, more preferably, fromabout 0.1% to about 0.3% by weight of the usage composition.

Builders

The compositions according to the present invention can further comprisea builder or builder system, especially for detergent compositions. Anyconventional builder system is suitable for use herein includingaluminosilicate materials, silicates, polycarboxylates, alkyl- oralkenyl-succinic acid and fatty acids, materials such as ethylenediaminetetraacetate, diethylene triamine pentamethyleneacetate, metal ionsequestrants such as aminopolyphosphonates, particularly ethylenediaminetetramethylene phosphonic acid and diethylene triaminepentamethylenephosphonic acid. Phosphate builders can also be usedherein.

The present invention can include a suitable builder or detergency salt.The level of detergent salt/builder can vary widely depending upon theend use of the composition and its desired physical form. When present,the compositions will typically comprise at least about 1% builder andmore typically from about 10% to about 80%, even more typically fromabout 15% to about 50% by weight, of the builder. Lower or higherlevels, however, are not meant to be excluded.

Inorganic or P-containing detergent salts include, but are not limitedto, the alkali metal, ammonium and alkanolammonium salts ofpolyphosphates (exemplified by the tripolyphosphates, pyrophosphates,and glassy polymeric meta-phosphates), phosphonates, phytic acid,silicates, carbonates (including bicarbonates and sesquicarbonates),sulphates, and aluminosilicates. However, non-phosphate salts arerequired in some locales. Importantly, the compositions herein functionsurprisingly well even in the presence of the so-called “weak” builders(as compared with phosphates) such as citrate, or in the so-called“underbuilt” situation that may occur with zeolite or layered silicatebuilders.

Organic detergent builders suitable for the purposes of the presentinvention include, but are not restricted to, a wide variety ofpolycarboxylate compounds. As used herein, “polycarboxylate” refers tocompounds having a plurality of carboxylate groups, preferably at least3 carboxylates. Polycarboxylate builder can generally be added to thecomposition in acid form, but can also be added in the form of aneutralized salt. When utilized in salt form, alkali metals, such assodium, potassium, and lithium, or alkanolammonium salts are preferred.

Examples of suitable silicate builders, carbonate salts, aluminosilicatebuilders, polycarboxylate builders, citrate builders,3,3-dicarboxy-4-oxa-1,6-hexanedioate builders and related compoundsdisclosed in U.S. Pat. No. 4,566,984, to Bush, succinic acid builders,phosphorous-based builders and fatty acids, are disclosed in U.S. Pat.Nos. 5,576,282, 5,728,671 and 5,707,950.

Additional suitable builders can be an inorganic ion exchange material,commonly an inorganic hydrated aluminosilicate material, moreparticularly a hydrated synthetic zeolite such as hydrated zeolite A, X,B, HS or MAP.

Specific polycarboxylates suitable for the present invention arepolycarboxylates containing one carboxy group include lactic acid,glycolic acid and ether derivatives thereof as disclosed in BelgianPatent Nos. 831,368, 821,369 and 821,370. Polycarboxylates containingtwo carboxy groups include the water-soluble salts of succinic acid,malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycollicacid, tartaric acid, tartronic acid and fumaric acid, as well as theether carboxylates described in German Offenlegenschrift 2,446,686, and2,446,687 and U.S. Pat. No. 3,935,257 and the sulfinyl carboxylatesdescribed in Belgian Patent No. 840,623. Polycarboxylates containingthree carboxy groups include, in particular, water-soluble citrates,aconitrates and citraconates as well as succinate derivatives such asthe carboxymethyloxysuccinates described in British Patent No.1,379,241, lactoxysuccinates described in Netherlands Application7205873, and the oxypolycarboxylate materials such as2-oxa-1,1,3-propane tricarboxylates described in British Patent No.1,387,447.

Polycarboxylates containing four carboxy groups include oxydisuccinatesdisclosed in British Patent No. 1,261,829, 1,1,2,2-ethanetetracarboxylates, 1,1,3,3-propane tetracarboxylates and 1,1,2,3-propanetetracarboxylates. Polycarboxylates containing sulfo substituentsinclude the sulfosuccinate derivatives disclosed in British Patent Nos.1,398,421 and 1,398,422 and in U.S. Pat. No. 3,936,448, and thesulfonated pyrolysed citrates described in British Patent No. 1,082,179,while polycarboxylates containing phosphone substituents are disclosedin British Patent No. 1,439,000.

Alicyclic and heterocyclic polycarboxylates includecyclopentane-cis,cis,cis-tetracarboxylates, cyclopentadienidepentacarboxylates, 2,3,4,5-tetrahydro-furan-cis, cis,cis-tetracarboxylates, 2,5-tetrahydro-furan-cis-dicarboxylates,2,2,5,5-tetrahydrofuran-tetracarboxylates,1,2,3,4,5,6-hexane-hexacarboxylates and carboxymethyl derivatives ofpolyhydric alcohols such as sorbitol, mannitol and xylitol. Aromaticpoly-carboxylates include mellitic acid, pyromellitic acid and thephthalic acid derivatives disclosed in British Patent No. 1,425,343.

Of the above, the preferred polycarboxylates are hydroxycarboxylatescontaining up to three carboxy groups per molecule, more particularlycitrates.

Preferred builder systems for use in the present compositions include amixture of a water-insoluble aluminosilicate builder such as zeolite Aor of a layered silicate (SKS6), and a water-soluble carboxylatechelating agent such as citric acid.

Preferred builder systems include a mixture of a water-insolublealuminosilicate builder such as zeolite A, and a water solublecarboxylate chelating agent such as citric acid. Preferred buildersystems for use in liquid detergent compositions of the presentinvention are soaps and polycarboxylates.

Other suitable water-soluble organic salts are the homo- or copolymericacids or their salts, in which the polycarboxylic acid comprises atleast two carboxyl radicals separated from each other by not more thantwo carbon atoms. Polymers of this type are disclosed in GB-A-1,596,756.Examples of such salts are polyacrylates of MW 2000–5000 and theircopolymers with maleic anhydride, such copolymers having a molecularweight of from 20,000 to 70,000, especially about 40,000.

Detergency builder salts are normally included in amounts of from 5% to80% by weight of the composition preferably from 10% to 70% and mostusually from 30% to 60% by weight.

Bleaching Agent

Additional optional detergent ingredients that can be included in thedetergent compositions of the present invention include bleaching agentssuch as hydrogen peroxide, PB1, PB4 and percarbonate with a particlesize of 400–800 microns. These bleaching agent components can includeone or more oxygen bleaching agents and, depending upon the bleachingagent chosen, one or more bleach activators. When present oxygenbleaching compounds will typically be present at levels of from about 1%to about 25%.

The bleaching agent component for use herein can be any of the bleachingagents useful for detergent compositions including oxygen bleaches aswell as others known in the art. The bleaching agent suitable for thepresent invention can be an activated or non-activated bleaching agent.

Examples of suitable bleaching agents are disclosed in U.S. Pat. Nos.5,707,950 and 5,576,282.

The hydrogen peroxide releasing agents can be used in combination with,for example, the bleach activators disclosed in U.S. Pat. No. 5,707,950or Phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA⁻ OBS),described in WO94/28106), which are perhydrolyzed to form a peracid asthe active bleaching species, leading to improved bleaching effect. Alsosuitable activators are acylated citrate esters.

Useful bleaching agents, including peroxyacids and bleaching systemscomprising bleach activators and peroxygen bleaching compounds for usein detergent compositions according to the invention are described inWO95/27772, WO95/27773, WO95/27774, WO95/27775 and U.S. Pat. No.5,707,950.

Metal-containing catalysts for use in bleach compositions, includecobalt-containing catalysts such as pentamine acetate cobalt(III) saltsand manganese-containing catalysts such as those described in EPA 549271; EPA 549 272; EPA 458 397; U.S. Pat. No. 5,246,621; EPA 458 398;U.S. Pat. No. 5,194,416 and U.S. Pat. No. 5,114,611. Bleachingcomposition comprising a peroxy compound, a manganese-containing bleachcatalyst and a chelating agent is described in the patent application No94870206.3. All of the above patents and applications being incorporatedherein by reference.

Dye Transfer Inhibiting Agents

The fabric care compositions of the present invention can also includecompounds for inhibiting dye transfer from one fabric to another ofsolubilized and suspended dyes encountered during fabric laundering andconditioning operations involving colored fabrics.

Polymeric Dye Transfer Inhibiting Agents

The fabric care compositions according to the present invention can alsocomprise from 0.001% to 10%, preferably from 0.01% to 2%, morepreferably from 0.05% to 1% by weight of polymeric dye transferinhibiting agents. Said polymeric dye transfer inhibiting agents arenormally incorporated into fabric care compositions in order to inhibitthe transfer of dyes from colored fabrics onto fabrics washed therewith.These polymers have the ability to complex or adsorb the fugitive dyeswashed out of dyed fabrics before the dyes have the opportunity tobecome attached to other articles in the wash or the rinse.

Especially suitable polymeric dye transfer inhibiting agents arepolyvinylpyrrolidone polymers, poly(4-vinylpyridine-N-oxide), polyamineN-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof.Examples of such dye transfer inhibiting agents are disclosed in U.S.Pat. No. 5,804,219, issued Sep. 8, 1998 to T. Trinh, S. L.-L. Sung, H.B. Tordil, and P. A. Wendland, and in U.S. Pat. Nos. 5,707,950 and5,707,951, all are incorporated herein by reference.

Additional suitable dye transfer inhibiting agents include, but are notlimited to, cross-linked polymers. Cross-linked polymers are polymerswhose backbone are interconnected to a certain degree; these links canbe of chemical or physical nature, possibly with active groups n thebackbone or on branches; cross-linked polymers have been described inthe Journal of Polymer Science, volume 22, pages 1035–1039.

In one embodiment, the cross-linked polymers are made in such a way thatthey form a three-dimensional rigid structure, which can entrap dyes inthe pores formed by the three-dimensional structure. In anotherembodiment, the cross-linked polymers entrap the dyes by swelling.

Such cross-linked polymers are described in the co-pending Europeanpatent application 94870213.9.

Chlorine Scavenging Agents

Chlorine scavenging agents are actives that react with chlorine, or withchlorine-generating materials, such as hypochlorite, to eliminate orreduce the bleaching activity of the chlorine materials. Chlorine isused in many parts of the world to sanitize water. To make sure that thewater is safe, a small amount, typically about 1 to 2 ppm of chlorine isleft in the water. It has been found that this small amount of chlorinein the tap water can cause fading of some fabric dyes. For rinse-addedcompositions, it is suitable to incorporate enough chlorine scavengingagent to neutralize about 1 ppm, preferably 2 ppm, more preferably 3ppm, and even more preferably 10 ppm of chlorine in rinse water.

Suitable levels of the optional chlorine scavengers in the rinse-addedcomposition of the present invention range from about 0.01% to about10%, preferably from about 0.02% to about 5%, more preferably from about0.05% to about 4%.

The fabric softener compositions, and especially the preferredcompositions herein, can contain an effective amount of chlorinescavenger, preferably selected from the group consisting of:

-   -   a. amines and their salts;    -   b. ammonium salts;    -   c. amino acids and their salts;    -   d. polyamino acids and their salts;    -   e. polyethyleneimines and their salts;    -   f. polyamines and their salts;    -   g. polyamineamides and their salts;    -   h. polyacrylamides; and    -   i. mixtures thereof.

Non-limiting examples of chlorine scavengers include amines, preferablyprimary and secondary amines, including primary and secondary fattyamines, and alkanolamines; and their salts; ammonium salts, e.g.,chloride, bromide, citrate, sulfate; amine-functional polymers and theirsalts; amino acid homopolymers with amino groups and their salts, suchas polyarginine, polylysine, polyhistidine; amino acid copolymers withamino groups and their salts, including1,5-di-ammonium-2-methyl-panthene dichloride and lysinemonohydrochloride; amino acids and their salts, preferably those havingmore than one amino group per molecule, such as arginine, histidine, andlysine, reducing anions such as sulfite, bisulfite, thiosulfate, andnitrite. antioxidants such as ascorbate, carbamate, phenols; andmixtures thereof.

Preferred chlorine scavengers are water soluble, especially, lowmolecular weight primary and secondary amines of low volatility, e.g.,monoethanolamine, diethanolamine, tris(hydroxymethyl)aminomethane,hexamethylenetetramine, and their salts, and mixtures thereof. Suitablechlorine scavenger polymers include: water soluble amine-functionalpolymers, e.g., polyethyleneimines, polyamines, polyamineamides,polyacrylamides, and their salts, and mixtures thereof. The preferredpolymers are polyethyleneimines; the polyamines, including, e.g.,di(higher alkyl)cyclic amines and their condensation products, andpolymers containing amino groups; polyamineamides, and their salts; andmixtures thereof. Preferred polymers for use in the fabric softeningcompositions of the present invention are polyethyleneimines and theirsalts. Preferred polyethyleneimines have a molecular weight of less thanabout 2000, more preferably from about 200 to about 1500. The watersolubility is preferably at least about 1 g/100 g water, more preferablyat least about 3 g/100 g water, even more preferably at least about 5g/100 g water.

Some polyamines with the general formula (R¹)₂N(CX₂)_(n)N(R²)₂ can serveboth as a chlorine scavenging agent and a “chelant” color care agent.Non-limiting examples of such preferred polyamines areN,N,N′,N′-tetrakis(2-hydroxypropyl) ethylenediamine andN,N,N′,N″,N″-penta(2-hydroxypropyl)diethylenetriamine.

Preferred polymeric chlorine scavengers have an average molecular weightof less than about 5,000, more preferably from about 200 to about 2,000,even more preferably from about 200 to about 1,000. Low molecular weightpolymers are easier to remove from fabrics than higher molecular weightpolymers, resulting in less buildup of the chlorine scavenger andtherefore less discoloration of the fabrics. Liquid chlorine scavengerscan be used in liquid softener compositions, but amine-functionalchlorine scavengers are preferably neutralized by an acid, before theyare added into the compositions.

Polymeric Soil Release Agents

Soil release agents, usually polymers, are especially desirableadditives at levels of from about 0.05% to about 5%, preferably fromabout 0.1% to about 4%, more preferably from about 0.2% to about 3%.Suitable soil release agents are disclosed in U.S. Pat. No. 4,702,857,Gosselink, issued Oct. 27, 1987; U.S. Pat. No. 4,711,730, Gosselink andDiehl, issued Dec. 8, 1987; U.S. Pat. No. 4,713,194, Gosselink issuedDec. 15, 1987; U.S. Pat. No. 4,877,896, Maldonado, Trinh, and Gosselink,issued Oct. 31, 1989; U.S. Pat. No. 4,956,447, Gosselink, Hardy, andTrinh, issued Sep. 11, 1990; and U.S. Pat. No. 4,749,596, Evans,Huntington, Stewart, Wolf, and Zimmerer, issued Jun. 7, 1988, saidpatents being incorporated herein by reference.

Especially desirable optional ingredients are polymeric soil releaseagents comprising block copolymers of polyalkylene terephthalate andpolyoxyethylene terephthalate, and block copolymers of polyalkyleneterephthalate and polyethylene glycol. The polyalkylene terephthalateblocks preferably comprise ethylene and/or propylene groups. Many suchsoil release polymers are nonionic.

A preferred nonionic soil release polymer has the following averagestructure:CH₃O(CH₂CH₂O)₄₀—[C(O)—C₆H₄—C(O)—OCH₂CH(CH₃)O—]₅—C(O)—C₆H₄—C(O)—(OCH₂CH₂—)₄₀OCH₃.

Such soil release polymers are described in U.S. Pat. No. 4,849,257,Borcher, Trinh and Bolich, issued Jul. 18, 1989, said patent beingincorporated herein by reference.

Another highly preferred nonionic soil release polymer is described inNew Zealand Pat. No. 242,150, issued Aug. 7, 1995 to Pan, Gosselink, andHonsa, said patent is incorporated herein by reference.

The polymeric soil release agents useful in the present invention caninclude anionic and cationic polymeric soil release agents. Suitableanionic polymeric or oligomeric soil release agents are disclosed inU.S. Pat. No. 4,018,569, Trinh, Gosselink and Rattinger, issued Apr. 4,1989, said patent being incorporated herein by reference. Other suitablepolymers are disclosed in U.S. Pat. No. 4,808,086, Evans, Huntington,Stewart, Wolf, and Zimmerer, issued Feb. 24, 1989, said patent beingincorporated herein by reference. Suitable cationic soil releasepolymers are described in U.S. Pat. No. 4,956,447, Gosselink, Hardy, andTrinh, issued Sep. 11, 1990, said patent being incorporated hereinbeforeby reference.

Dye Fixing Agents

The optional dye fixing agents, or “fixatives”, are materials which areuseful to improve the appearance of dyed fabrics by minimizing the lossof dye from fabrics due to washing.

Many dye fixing agents are cationic, and are based on quaternizednitrogen compound or on nitrogen compounds having a strong cationiccharge which is formed in situ under the conditions of usage. Cationicfixatives are available under various trade names from severalsuppliers. Representative examples include: CROSCOLOR® PMF andCROSCOLOR® NOFF available from Crosfield; INDOSOL® E-50(polyethyleneamine-based) and SANDOFIX® TPS from Sandoz; and CARTAFIX®CB from Clariant. Additional non-limiting examples include SANDOFIX SWE(a cationic resinous compound) from Sandoz; REWIN® SRF, REWIN® SRF-O andREWIN DWR from CHT-Beitlich GMBH; Tinofix® ECO, Tinofix® FRD and Solfin®from Ciba-Geigy. Preferred optional dye fixing agents for use in thecompositions of the present invention are SANDOFIX TPS and CARTAFIX CB.

Other cationic dye fixing agents are described in “Aftertreatments forImproving the Fastness of Dyes on Textile Fibres”, Christopher C. Cook,Rev. Prog. Coloration, Vol. XII, (1982). Optional dye fixing agentssuitable for use in the present invention are ammonium compounds such asfatty acid-diamine condensates inter alia the hydrochloride, acetate,metosulphate and benzyl hydrochloride salts of diamine esters.Non-limiting examples include oleyldiethyl aminoethylamide, oleylmethyldiethylenediamine methosulphate, monostearylethylenediaminotrimethylammonium methosulphate. In addition, the N-oxides oftertiary amines; derivatives of polymeric alkyldiamines,polyamine-cyanuric chloride condensates, and aminated glyceroldichlorohydrins are suitable for use as dye fixatives in thecompositions of the present invention.

Another class of optional dye fixing agents suitable for use in thepresent invention are cellulose reactive dye fixing agents. Thecellulose reactive dye fixatives may be suitably combined with one ormore dye fixatives described herein above in order to comprise a “dyefixative system”.

The term “cellulose reactive dye fixing agent” is defined herein as “adye fixative agent which reacts with the cellulose fibers uponapplication of heat or upon a heat treatment either in situ or by theformulator”.

Typically cellulose reactive dye fixing agents are compounds whichcontain a cellulose reactive moiety. Non limiting examples of thesecompounds include halogeno-triazines, vinyl sulphones, epichlorhydrinederivatives, hydroxyethylene urea derivatives, formaldehyde condensationproducts, polycarboxylates, glyoxal and glutaraldehyde derivatives, andmixtures thereof. Further examples can be found in “Textile Processingand Properties”, Tyrone L. Vigo, at page 120 to 121, Elsevier (1997),which discloses specific electrophilic groups and their correspondingcellulose affinity.

Preferred hydroxyethylene urea derivatives include dimethyloldihydroxyethylene, urea, and dimethyl urea glyoxal. Preferred formaldehydecondensation products include the condensation products derived fromformaldehyde and a group selected from an amino-group, an imino-group, aphenol group, an urea group, a cyanamide group and an aromatic group.Commercially available compounds among this class are Sandofix WE 56from Clariant, Zetex E from Zeneca and Levogen BF from Bayer. Preferredpolycarboxylates derivatives include butane tetracarboxilic acidderivatives, citric acid derivatives, polyacrylates and derivativesthereof. A referred cellulosic reactive dye fixing agent is Indosol CR(hydroxyethylene urea derivative) from Clariant. Other preferredcellulosic reactive dye fixing agents are Rewin DWR and Rewin WBS fromCHT R. Beitlich.

The compositions of the present invention optionally comprise from about0.001% to about 40%, preferably from about 0.5% to more preferably toabout 10%, more preferably from about 1% to about 5%, by weight of thefabric care composition, of one or more dye fixing agents.

Dispersants

The detergent composition of the present invention can also containdispersants. Suitable water-soluble organic salts are the homo- orco-polymeric acids or their salts, in which the polycarboxylic acidcomprises at least two carboxyl radicals separated from each other bynot more than two carbon atoms.

Polymers of this type are disclosed in GB-A-1,596,756. Examples of suchsalts are polyacrylates of MW 2000–5000 and their copolymers with maleicanhydride, such copolymers having a molecular weight of from 1,000 to100,000.

Especially, copolymer of acrylate and methylacrylate such as the 480Nhaving a molecular weight of 4000, at a level from 0.5–20% by weight ofcomposition can be added in the detergent compositions of the presentinvention.

The compositions of the invention can contain a lime soap peptisercompound, which has a lime soap dispersing power (LSDP), as definedhereinafter of no more than 8, preferably no more than 7, mostpreferably no more than 6. The lime soap peptiser compound is preferablypresent at a level from 0% to 20% by weight.

A numerical measure of the effectiveness of a lime soap peptiser isgiven by the lime soap dispersant power (LSDP) which is determined usingthe lime soap dispersant test as described in an article by H. C.Borghetty and C. A. Bergman, J. Am. Oil. Chem. Soc., volume 27, pages88–90, (1950). This lime soap dispersion test method is widely used bypractitioners in this art field being referred to, for example, in thefollowing review articles; W. N. Linfield, Surfactant science Series,Volume 7, page 3; W. N. Linfield, Tenside surf. det., volume 27, pages159–163, (1990); and M. K. Nagarajan, W. F. Masler, Cosmetics andToiletries, volume 104, pages 71–73, (1989). The LSDP is the % weightratio of dispersing agent to sodium oleate required to disperse the limesoap deposits formed by 0.025 g of sodium oleate in 30 ml of water of333 ppm CaCO₃ (Ca:Mg=3:2) equivalent hardness.

Surfactants having good lime soap peptizer capability will includecertain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates andethoxylated alcohols.

Exemplary surfactants having a LSDP of no more than 8 for use in accordwith the present invention include C₁₆–C₁₈ dimethyl amine oxide, C₁₂–C₁₈alkyl ethoxysulfates with an average degree of ethoxylation of from 1–5,particularly C₁₂–C₁₅ alkyl ethoxysulfate surfactant with a degree ofethoxylation of amount 3 (LSDP=4), and the C₁₄–C₁₅ ethoxylated alcoholswith an average degree of ethoxylation of either 12 (LSDP=6) or 30, soldunder the tradenames Lutensol A012 and Lutensol A030 respectively, byBASF GmbH.

Polymeric lime soap peptizers suitable for use herein are described inthe article by M. K. Nagarajan, W. F. Masler, to be found in Cosmeticsand Toiletries, volume 104, pages 71–73, (1989).

Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyl]benzenesulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate,4-[N-decanoyl-6-aminohexanoyl]benzene sulfonate and mixtures thereof;and nonanoyloxy benzene sulfonate together with hydrophilic/hydrophobicbleach formulations can also be used as lime soap peptizers compounds.

Examples of other suitable dispersing agents are disclosed in U.S. Pat.Nos. 5,576,282 and 5,728,671.

Enzymes

Optional enzymes are useful in the compositions, especially wash-addedand rinse-added compositions, of the present invention to improvecleaning, odor control and/or fabric appearance benefits. Preferredenzymes include laundry detergent and/or fabric care applicable enzymeslike protease, amylase, lipase, cutinase and/or cellulase.

Examples of suitable enzymes are disclosed in U.S. Pat. Nos. 5,576,282,5,728,671 and 5,707,950.

Particularly useful proteases are described in PCT publications: WO95/30010 published Nov. 9, 1995 by The Procter & Gamble Company; WO95/30011 published Nov. 9, 1995 by The Procter & Gamble Company; and WO95/29979 published Nov. 9, 1995 by The Procter & Gamble Company.

In addition to the peroxidase enzymes disclosed in U.S. Pat. Nos.5,576,282, 5,728,671 and 5,707,950, other suitable peroxidase enzymesare disclosed in European Patent application EP No. 96870013.8, filedFeb. 20, 1996. Also suitable is the laccase enzyme.

Preferred enhancers are substituted phenthiazine and phenoxasine10-Phenothiazinepropionicacid (PPT), 10-ethylphenothiazine-4-carboxylicacid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine(described in WO 94/12621) and substituted syringates (C3–C5 substitutedalkyl syringates) and phenols. Sodium percarbonate or perborate arepreferred sources of hydrogen peroxide.

Said peroxidases are normally incorporated in the detergent compositionat levels from 0.0001% to 2% of active enzyme by weight of the detergentcomposition.

Other preferred enzymes that can be included in the fabric care ordetergent compositions of the present invention include lipases.Suitable lipase enzymes for detergent usage include those produced bymicroorganisms of the Pseudomonas group, such as Pseudomonas stutzeriATCC 19.154, as disclosed in British Patent 1,372,034. Suitable lipasesinclude those which show a positive immunological cross-reaction withthe antibody of the lipase, produced by the microorganism Pseudomonasfluorescent IAM 1057. This lipase is available from Amano PharmaceuticalCo. Ltd., Nagoya, Japan, under the trade name Lipase P “Amano,”hereinafter referred to as “Amano-P”. Other suitable commercial lipasesinclude Amano-CES, lipases ex Chromobacter viscosum, e.g. Chromobacterviscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan;Chromobacter viscosum lipases from U.S. Biochemical Corp., U.S.A. andDisoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli.Especially suitable lipases are lipases such as M1 Lipase^(R) andLipomax^(R) (Gist-Brocades) and Lipolase^(R) and LipolaseUltra^(R)(Novo) which have found to be very effective when used incombination with the compositions of the present invention.

Also suitable are cutinases [EC 3.1.1.50] which can be considered as aspecial kind of lipase, namely lipases which do not require interfacialactivation. Addition of cutinases to detergent compositions have beendescribed in e.g. WO 88/09367 (Genencor).

The lipases and/or cutinases are normally incorporated in the detergentcomposition at levels from 0.0001% to 2% of active enzyme by weight ofthe detergent composition.

Known amylases (α and/or β) can be included for removal ofcarbohydrate-based stains. WO 94/02597, Novo Nordisk A/S published Feb.3, 1994, describes cleaning compositions which incorporate mutantamylases. See also WO94/18314, Genencor, published Aug. 18, 1994 andWO95/10603, Novo Nordisk A/S, published Apr. 20, 1995. Other amylasesknown for use in detergent compositions include both α- and β-amylases.α-Amylases are known in the art and include those disclosed in U.S. Pat.No. 5,003,257; EP 252,666; WO 91/00353; FR 2,676,456; EP 285,123; EP525,610; EP 368,341; and British Patent Specification No. 1,296,839(Novo). Other suitable amylase are stability-enhanced amylases includingPurafact Ox Am^(R) described in WO 94/18314, published Aug. 18, 1994 andWO96/05295, Genencor, published Feb. 22, 1996 and amylase variants fromNovo Nordisk A/S, disclosed in WO 95/10603, published April 95.

Examples of commercial α-amylases products are TERMAMYL®, BAN®,FUNGAMYL® and DURAMYL®, all available from Novo Nordisk A/S Denmark.WO95/26397 describes other suitable amylases: α-amylases characterisedby having a specific activity at least 25% higher than the specificactivity of TERMAMYL® at a temperature range of 25° C. to 55° C. and ata pH value in the range of 8 to 10, measured by the PHADEBAS® α-amylaseactivity assay. Other amylolytic enzymes with improved properties withrespect to the activity level and the combination of thermostability anda higher activity level are described in WO95/35382.

The cellulases usable in the present invention include both bacterial orfungal cellulases. Preferably, they will have a pH optimum of between 5and 12 and an activity above 50 CEVU (Cellulose Viscosity Unit).Suitable cellulases are disclosed in U.S. Pat. No. 4,435,307,Barbesgoard et al, J61078384 and WO96/02653 which discloses fungalcellulase produced respectively from Humicola insolens, Trichoderma,Thielavia and Sporotrichum. EP 739 982 describes cellulases isolatedfrom novel Bacillus species. Suitable cellulases are also disclosed inGB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832 and WO95/26398.

Examples of such cellulases are cellulases produced by a strain ofHumicola insolens (Humicola grisea var. thermoidea), particularly theHumicola strain DSM 1800. Other suitable cellulases are cellulasesoriginated from Humicola insolens having a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415 amino acids; and a^(˜)43 kD endoglucanase derived from Humicola insolens, DSM 1800,exhibiting cellulase activity; a preferred endoglucanase component hasthe amino acid sequence disclosed in PCT Patent Application No. WO91/17243. Also suitable cellulases are the EGIII cellulases fromTrichoderma longibrachiatum described in WO94/21801, Genencor, publishedSep. 29, 1994. Especially suitable cellulases are the cellulases havingcolor care benefits. Examples of such cellulases are cellulasesdescribed in European patent application No. 91202879.2, filed Nov. 6,1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A/S) are especiallyuseful. See also WO91/17244 and WO91/21801. Other suitable cellulasesfor fabric care and/or cleaning properties are described in WO96/34092,WO96/17994 and WO95/24471. Suitable cellulases and their appropriatelevels useful in rinse-added compositions of the present invention aredescribed in U.S. Pat. No. 5,445,747, issued Aug. 29, 1995 to L. L.Kvietok, T. Trinh and J. A. Hollingshead. All these patents areincorporated herein by reference.

Said cellulases are normally incorporated in the detergent compositionat levels from 0.0001% to 2% of active enzyme by weight of the detergentcomposition.

The above-mentioned enzymes can be of any suitable origin, such asvegetable, animal, bacterial, fungal and yeast origin. Purified ornon-purified forms of these enzymes can be used. Also included bydefinition, are mutants of native enzymes. Mutants can be obtained e.g.by protein and/or genetic engineering, chemical and/or physicalmodifications of native enzymes. Common practice as well is theexpression of the enzyme via host organisms in which the geneticmaterial responsible for the production of the enzyme has been cloned.

Enzymes are normally incorporated in the detergent composition at levelsfrom 0.0001% to 2% of active enzyme by weight of the detergentcomposition. The enzymes can be added as separate single ingredients(prills, granulates, stabilized liquids, etc. containing one enzyme) oras mixtures of two or more enzymes (e.g. cogranulates).

Other suitable detergent ingredients that can be added are enzymeoxidation scavengers. Examples of such enzyme oxidation scavengers areethoxylated tetraethylene polyamines.

A range of enzyme materials and means for their incorporation intosynthetic detergent compositions is also disclosed in WO 9307263 and WO9307260 to Genencor International, WO 8908694 to Novo, and U.S. Pat. No.3,553,139, Jan. 5, 1971 to McCarty et al. Enzymes are further disclosedin U.S. Pat. No. 4,101,457, Place et al, Jul. 18, 1978, and in U.S. Pat.No. 4,507,219, Hughes, Mar. 26, 1985. Enzyme materials useful for liquiddetergent formulations, and their incorporation into such formulations,are disclosed in U.S. Pat. No. 4,261,868, Hora et al, Apr. 14, 1981.Enzymes for use in detergents can be stabilized by various techniques.Enzyme stabilization techniques are disclosed and exemplified in U.S.Pat. No. 3,600,319, Aug. 17, 1971, Gedge et al, EP 199,405 and EP200,586, Oct. 29, 1986, Venegas. Enzyme stabilization systems are alsodescribed, for example, in U.S. Pat. No. 3,519,570. A useful Bacillus,sp. AC13 giving proteases, xylanases and cellulases, is described in WO9401532 to Novo.

Enzymes can also be used to control certain types of malodor, especiallymalodor from urine and other types of excretions, including regurgitatedmaterials. Proteases are especially desirable. The activity ofcommercial enzymes depends very much on the type and purity of theenzyme being considered. Enzymes that are water soluble proteases likepepsin, tripsin, ficin, bromelin, papain, rennin, and mixtures thereofare particularly useful.

For odor control purpose, enzymes are normally incorporated at levelssufficient to provide up to about 5 mg by weight, preferably from about0.001 mg to about 3 mg, more preferably from about 0.002 mg to about 1mg, of active enzyme per gram of the aqueous compositions. Statedotherwise, the aqueous compositions herein can comprise from about0.0001% to about 0.5%, preferably from about 0.001% to about 0.3%, morepreferably from about 0.005% to about 0.2% by weight of a commercialenzyme preparation. Protease enzymes are usually present in suchcommercial preparations at levels sufficient to provide from 0.0005 to0.1 Anson units (AU) of activity per gram of aqueous composition.

Nonlimiting examples of suitable, commercially available, water solubleproteases are pepsin, tripsin, ficin, bromelin, papain, rennin, andmixtures thereof. Papain can be isolated, e.g., from papaya latex, andis available commercially in the purified form of up to, e.g., about 80%protein, or cruder, technical grade of much lower activity. Othersuitable examples of proteases are the subtilisins which are obtainedfrom particular strains of B. subtilis and B. licheniforms. Anothersuitable protease is obtained from a strain of Bacillus, having maximumactivity throughout the pH range of 8–12, developed and sold by NovoIndustries A/S under the registered trade name ESPERASE®. Thepreparation of this enzyme and analogous enzymes is described in BritishPatent Specification No. 1,243,784 of Novo. Proteolytic enzymes suitablefor removing protein-based stains that are commercially availableinclude those sold under the trade names ALCALASE® and SAVINASE® by NovoIndustries A/S (Denmark) and MAXATASE® by International Bio-Synthetics,Inc. (The Netherlands). Other proteases include Protease A (see EuropeanPatent Application 130,756, published Jan. 9, 1985); Protease B (seeEuropean Patent Application Serial No. 87303761.8, filed Apr. 28, 1987,and European Patent Application 130,756, Bott et al, published Jan. 9,1985); and proteases made by Genencor International, Inc., according toone or more of the following patents: Caldwell et al, U.S. Pat. Nos.5,185,258, 5,204,015 and 5,244,791.

A wide range of enzyme materials and means for their incorporation intoliquid compositions are also disclosed in U.S. Pat. No. 3,553,139,issued Jan. 5, 1971 to McCarty et al. Enzymes are further disclosed inU.S. Pat. No. 4,101,457, Place et al, issued Jul. 18, 1978, and in U.S.Pat. No. 4,507,219, Hughes, issued Mar. 26, 1985. Other enzyme materialsuseful for liquid formulations, and their incorporation into suchformulations, are disclosed in U.S. Pat. No. 4,261,868, Hora et al,issued Apr. 14, 1981. Enzymes can be stabilized by various techniques,e.g., those disclosed and exemplified in U.S. Pat. No. 3,600,319, issuedAug. 17, 1971 to Gedge, et al., European Patent Application PublicationNo. 0 199 405, Application No. 86200586.5, published Oct. 29, 1986,Venegas, and in U.S. Pat. No. 3,519,570. All of the above patents andapplications are incorporated herein, at least in pertinent part.

Enzyme-polyethylene glycol conjugates are also preferred. Suchpolyethylene glycol (PEG) derivatives of enzymes, wherein the PEG oralkoxy-PEG moieties are coupled to the protein molecule through, e.g.,secondary amine linkages. Suitable derivatization decreasesimmunogenicity, thus minimizes allergic reactions, while stillmaintaining some enzymatic activity. An example of protease-PEG's isPEG-subtilisin Carlsberg from B. lichenniformis coupled to methoxy-PEGsthrough secondary amine linkage, and is available from Sigma-AldrichCorp., St. Louis, Mo.

Heavy Metal Chelating Agents

The wash-added fabric care compositions herein can also optionallycontain one or more iron and/or manganese chelating agents. Suitablechelating agents is selected from the group consisting of aminocarboxylates, amino phosphonates, polyfunctionally-substituted aromaticchelating agents and mixtures thereof. The chelating agents disclosed insaid U.S. Pat. No. 5,759,990 at column 26, line 29 through column 27,line 38 are suitable. Other examples of suitable chelating agents aredisclosed in U.S. Pat. No. 5,728,671.

A suitable amine-based metal chelator that can be used herein isethylenediamine-N,N′-disuccinate (EDDS). EDDS is described in U.S. Pat.No. 4,704,233, and has the formula (shown in free acid form):HN(L)C₂H₄N(L)Hwherein L is a CH₂(COOH)CH₂(COOH) group.

The compositions herein can also contain water-soluble methyl glycinediacetic acid (MGDA) salts (or acid form) as a chelant or co-builderuseful with, for example, insoluble builders such as zeolites, layeredsilicates and the like.

If utilized, these chelating agents will generally comprise from about0.1% to about 15% by weight of the detergent compositions herein. Morepreferably, if utilized, the chelating agents will comprise from about0.1% to about 3.0% by weight of such compositions.

For rinse-added compositions, preferred metal chelating agents containamine and especially tertiary amine moieties since these tend to befabric substantive and very effectively chelate copper and iron as wellas other metals. A preferred amine-based metal chelating compound foruse in compositions of the present invention has the following generalstructure:(R₁)(R₂)N(CX₂)_(n)N(R₃)(R₄)wherein X is selected from the group consisting of hydrogen, linear orbranched, substituted or unsubstituted alkyl having from 1 to 10 carbonsatoms and substituted or unsubstituted aryl having at least 6 carbonatoms; n is an integer from 0 to 6; R₁, R₂, R₃, and R₄ are independentlyselected from the group consisting of alkyl; aryl; alkaryl; arylalkyl;hydroxyalkyl; polyhydroxyalkyl; polyalkylether having the formula—((CH2)_(y)O)_(z)R₇ where R₇ is hydrogen or a linear, branched,substituted or unsubstituted alkyl chain having from 1 to 10 carbonatoms and where y is an integer from 2 to 10 and z is an integer from 1to 30; alkoxy; polyalkoxy having the formula: —(O(CH₂)_(y))_(z)R₇; thegroup —C(O)R₈ where R₈ is alkyl; alkaryl; arylalkyl; hydroxyalkyl;polyhydroxyalkyl and polyalkyether as defined in R₁, R₂, R₃, and R₄;(CX₂)_(n)N(R₅)(R₆) with no more than one of R₁, R₂, R₃, and R₄ being(CX₂)_(n)N(R₅)(R₆) and wherein R₅ and R₆ are alkyl; alkaryl; arylalkyl;hydroxyalkyl; polyhydroxyalkyl; polyalkylether; alkoxy and polyalkoxy asdefined in R₁, R₂, R₃, and R₄; and either of R₁+R₃ or R₄ or R₂+R₃ or R₄can combine to form a cyclic substituent.

Preferred chelating agents include those where R₁, R₂, R₃, and R₄ areindependently selected from the group consisting of alkyl groups havingfrom 1 to 10 carbon atoms and hydroxyalkyl groups having from 1 to 5carbon atoms, preferably ethyl, methyl, hydroxyethyl, hydroxypropyl andisohydroxypropyl. The preferred chelating agent has more than about 1%nitrogen by weight of the compound, and preferably more than 7%. Apreferred chelating agent is tetrakis-(2-hydroxylpropyl) ethylenediamine(TPED).

The rinse-added composition contains at least about 0.01%, preferably atleast about 0.05%, more preferably at least about 0.10% and less thanabout 10%, preferably less than about 5% and more preferably less thanabout 1% of chelating agent, by weight of the composition.

Suds Suppressor

Another optional ingredient is a suds suppressor, exemplified bysilicones, and silica-silicone mixtures. Examples of suitable sudssuppressors are disclosed in U.S. Pat. Nos. 5,707,950 and 5,728,671.These suds suppressors are normally employed at levels of from 0.001% to2% by weight of the composition, preferably from 0.01% to 1% by weight.

Aqueous Carrier

The preferred carrier of the present invention is water. The water whichis used can be distilled, deionized, or tap water. Water is the mainliquid carrier due to its low cost, availability, safety, andenvironmental compatibility. Aqueous solutions are preferred for wrinklecontrol and odor control.

Water is very useful for fabric wrinkle removal or reduction. Not to bebound by theory, it is believed that water breaks many intrafiber andinterfiber hydrogen bonds that keep the fabric in a wrinkle state. Italso swells, lubricates and relaxes the fibers- to help the wrinkleremoval process.

Water serves as the liquid carrier for the fabric care branchedpolysaccharide and other soluble and/or dispersible optionalingredients.

Water also serves as the liquid carrier for the cyclodextrins, andfacilitates the complexation reaction between the cyclodextrin moleculesand any malodorous molecules that are on the fabric when it is treated.The dilute aqueous solution also provides the maximum separation ofcyclodextrin molecules on the fabric and thereby maximizes the chancethat an odor molecule will interact with a cyclodextrin molecule. It hasrecently also been discovered that water has an unexpected odorcontrolling effect of its own. It has been discovered that the intensityof the odor generated by some polar, low molecular weight organicamines, acids, and mercaptans is reduced when the odor-contaminatedfabrics are treated with an aqueous solution. Not to be bound by theory,it is believed that water solubilizes and depresses the vapor pressureof these polar, low molecular weight organic molecules, thus reducingtheir odor intensity.

The level of liquid carrier in the compositions of the present inventionis typically greater than about 80%, preferably greater than about 90%,more preferably greater than about 95%, by weight of the composition.When a concentrated composition is used, the level of liquid carrier istypically from about 2% to about 98%, by weight of the composition,preferably from about 35% to about 97%, more preferably from about 60%to about 95%, by weight of the composition.

Optionally, in addition to water, the carrier can contain a lowmolecular weight organic solvent that is highly soluble in water, e.g.,ethanol, propanol, isopropanol, and the like, and mixtures thereof. Lowmolecular weight alcohols can help the treated fabric to dry faster. Theoptional solvent is also useful in the solubilization of some adjunctshape retention polymers described hereinbefore. The optional watersoluble low molecular weight solvent can be used at a level of up toabout 50%, typically from about 0.1% to about 25%, preferably from about2% to about 15%, more preferably from about 5% to about 10%, by weightof the total composition. Factors that need to consider when a highlevel of solvent is used in the composition are odor, flammability, andenvironment impact.

II. Article of Manufacture

The present invention also relates to an article of manufacturecomprising the fabric care composition in a package, in association withinstructions for how to use the composition to treat fabrics correctly,in order to obtain the desirable fabric care results, viz, wrinkleremoval and/or reduction, wrinkle resistance, fiberstrengthening/anti-wear, fabric wear reduction, fabric shrinkageprevention and/or reduction, fabric pill prevention and/or reduction,shrinkage prevention and/or reduction, fabric color maintenance, fabriccolor fading reduction, soiling prevention and/or reduction, and/orfabric shape retention, and mixtures thereof. A preferred article ofmanufacture comprises said composition in a spray dispenser, inassociation with instructions for how to use the composition to treatfabrics correctly, including, e.g., the manner and/or amount ofcomposition to spray, and the preferred ways of stretching and/orsmoothing of the fabrics to remove wrinkles, as will be described withmore detailed herein below. It is important that the instructions be assimple and clear as possible, so that using pictures and/or icons isdesirable.

Spray Dispenser

An article of manufacture herein comprises a spray dispenser. The fabriccare composition is placed into a spray dispenser in order to bedistributed onto the fabric. Said spray dispenser for producing a sprayof liquid droplets can be any of the manually activated means as isknown in the art, e.g. trigger-type, pump-type, non-aerosolself-pressurized, and aerosol-type spray means, for treating the fabriccare composition to small fabric surface areas and/or a small number ofgarments, as well as non-manually operated, powered sprayers forconveniently treating the wrinkle control composition to large fabricsurface areas and/or a large number of garments. The spray dispenserherein does not normally include those that will substantially foam theclear, aqueous fabric care composition. It has been found that theperformance is increased by providing smaller particle droplets.Desirably, the Sauter mean particle diameter is from about 10 μm toabout 120 μm, more preferably, from about 20 μm to about 100 μm.Dewrinkling benefits for example are improved by providing smallparticles (droplets), especially when the surfactant is present.

The spray dispenser can be an aerosol dispenser. Said aerosol dispensercomprises a container which can be constructed of any of theconventional materials employed in fabricating aerosol containers. Thedispenser must be capable of withstanding internal pressure in the rangeof from about 20 to about 110 p.s.i.g., more preferably from about 20 toabout 70 p.s.i.g. The one important requirement concerning the dispenseris that it be provided with a valve member which will permit the clear,aqueous fabric care composition contained in the dispenser to bedispensed in the form of a spray of very fine, or finely divided,particles or droplets. The aerosol dispenser utilizes a pressurizedsealed container from which the clear, aqueous fabric care compositionis dispensed through a special actuator/valve assembly under pressure.The aerosol dispenser is pressurized by incorporating therein a gaseouscomponent generally known as a propellant. Common aerosol propellants,e.g., gaseous hydrocarbons such as isobutane, and mixed halogenatedhydrocarbons, can be used. Halogenated hydrocarbon propellants such aschlorofluoro hydrocarbons have been alleged to contribute toenvironmental problems, and are not preferred. When cyclodextrin ispresent hydrocarbon propellants are not preferred, because they can formcomplexes with the cyclodextrin molecules thereby reducing theavailability of uncomplexed cyclodextrin molecules for odor absorption.Preferred propellants are compressed air, nitrogen, inert gases, carbondioxide, etc. A more complete description of commercially availableaerosol-spray dispensers appears in U.S. Pat. No. 3,436,772, Stebbins,issued Apr. 8, 1969; and U.S. Pat. No. 3,600,325, Kaufman et al., issuedAug. 17, 1971; both of said references are incorporated herein byreference.

Preferably the spray dispenser can be a self-pressurized non-aerosolcontainer having a convoluted liner and an elastomeric sleeve. Saidself-pressurized dispenser comprises a liner/sleeve assembly containinga thin, flexible radially expandable convoluted plastic liner of fromabout 0.010 to about 0.020 inch thick, inside an essentially cylindricalelastomeric sleeve. The liner/sleeve is capable of holding a substantialquantity of fabric care composition and of causing said composition tobe dispensed. A more complete description of self-pressurized spraydispensers can be found in U.S. Pat. No. 5,111,971, Winer, issued May12, 1992, and U.S. Pat. No. 5,232,126, Winer, issued Aug. 3, 1993; bothof said references are herein incorporated by reference. Another type ofaerosol spray dispenser is one wherein a barrier separates the fabriccare composition from the propellant (preferably compressed air ornitrogen), as disclosed in U.S. Pat. No. 4,260,110, issued Apr. 7, 1981,and incorporated herein by reference. Such a dispenser is available fromEP Spray Systems, East Hanover, N.J.

More preferably, the spray dispenser is a non-aerosol, manuallyactivated, pump-spray dispenser. Said pump-spray dispenser comprises acontainer and a pump mechanism which securely screws or snaps onto thecontainer. The container comprises a vessel for containing the aqueousfabric care composition to be dispensed.

The pump mechanism comprises a pump chamber of substantially fixedvolume, having an opening at the inner end thereof. Within the pumpchamber is located a pump stem having a piston on the end thereofdisposed for reciprocal motion in the pump chamber. The pump stem has apassageway there through with a dispensing outlet at the outer end ofthe passageway and an axial inlet port located inwardly thereof.

The container and the pump mechanism can be constructed of anyconventional material employed in fabricating pump-spray dispensers,including, but not limited to: polyethylene; polypropylene;polyethyleneterephthalate; blends of polyethylene, vinyl acetate, andrubber elastomer. A preferred container is made of clear, e.g.,polyethylene terephthalate. Other materials can include stainless steel.A more complete disclosure of commercially available dispensing devicesappears in: U.S. Pat. No. 4,895,279, Schultz, issued Jan. 23, 1990; U.S.Pat. No. 4,735,347, Schultz et al., issued Apr. 5, 1988; and U.S. Pat.No. 4,274,560, Carter, issued Jun. 23, 1981; all of said references areherein incorporated by reference.

Most preferably, the spray dispenser is a manually activatedtrigger-spray dispenser. Said trigger-spray dispenser comprises acontainer and a trigger both of which can be constructed of any of theconventional material employed in fabricating trigger-spray dispensers,including, but not limited to: polyethylene; polypropylene; polyacetal;polycarbonate; polyethyleneterephthalate; polyvinyl chloride;polystyrene; blends of polyethylene, vinyl acetate, and rubberelastomer. Other materials can include stainless steel and glass. Apreferred container is made of clear, e.g. polyethylene terephthalate.The trigger-spray dispenser does not incorporate a propellant gas intothe odor-absorbing composition, and preferably it does not include thosethat will foam the fabric care composition. The trigger-spray dispenserherein is typically one which acts upon a discrete amount of the fabriccare composition itself, typically by means of a piston or a collapsingbellows that displaces the composition through a nozzle to create aspray of thin liquid. Said trigger-spray dispenser typically comprises apump chamber having either a piston or bellows which is movable througha limited stroke response to the trigger for varying the volume of saidpump chamber. This pump chamber or bellows chamber collects and holdsthe product for dispensing. The trigger spray dispenser typically has anoutlet check valve for blocking communication and flow of fluid throughthe nozzle and is responsive to the pressure inside the chamber. For thepiston type trigger sprayers, as the trigger is compressed, it acts onthe fluid in the chamber and the spring, increasing the pressure on thefluid. For the bellows spray dispenser, as the bellows is compressed,the pressure increases on the fluid. The increase in fluid pressure ineither trigger spray dispenser acts to open the top outlet check valve.The top valve allows the product to be forced through the swirl chamberand out the nozzle to form a discharge pattern. An adjustable nozzle capcan be used to vary the pattern of the fluid dispensed.

For the piston spray dispenser, as the trigger is released, the springacts on the piston to return it to its original position. For thebellows spray dispenser, the bellows acts as the spring to return to itsoriginal position. This action causes a vacuum in the chamber. Theresponding fluid acts to close the outlet valve while opening the inletvalve drawing product up to the chamber from the reservoir.

A more complete disclosure of commercially available dispensing devicesappears in U.S. Pat. No. 4,082,223, Nozawa, issued Apr. 4, 1978; U.S.Pat. No. 4,161,288, McKinney, issued Jul. 17, 1985; U.S. Pat. No.4,434,917, Saito et al., issued Mar. 6, 1984; and U.S. Pat. No.4,819,835, Tasaki, issued Apr. 11, 1989; U.S. Pat. No. 5,303,867,Peterson, issued Apr. 19, 1994; all of said references are incorporatedherein by reference.

A broad array of trigger sprayers or finger pump sprayers are suitablefor use with the compositions of this invention. These are readilyavailable from suppliers such as Calmar, Inc., City of Industry, Calif.;CSI (Continental Sprayers, Inc.), St. Peters, Mo.; Berry Plastics Corp.,Evansville, Ind., a distributor of Guala® sprayers; or SeaquestDispensing, Cary, Ill.

The preferred trigger sprayers are the blue inserted Guala® sprayer,available from Berry Plastics Corp., or the Calmar TS800-1A®, TS1300®,and TS-800-2®, available from Calmar Inc., because of the fine uniformspray characteristics, spray volume, and pattern size. More preferredare sprayers with precompression features and finer spraycharacteristics and even distribution, such as Yoshino sprayers fromJapan. Any suitable bottle or container can be used with the triggersprayer, the preferred bottle is a 17 fl-oz. bottle (about 500 ml) ofgood ergonomics similar in shape to the Cinch® bottle. It can be made ofany materials such as high density polyethylene, polypropylene,polyvinyl chloride, polystyrene, polyethylene terephthalate, glass, orany other material that forms bottles. Preferably, it is made of highdensity polyethylene or clear polyethylene terephthalate.

For smaller fluid ounce sizes (such as 1 to 8 ounces), a finger pump canbe used with canister or cylindrical bottle. The preferred pump for thisapplication is the cylindrical Euromist II® from Seaquest Dispensing.More preferred are those with precompression features.

The article of manufacture herein can also comprise a non-manuallyoperated spray dispenser. By “non-manually operated” it is meant thatthe spray dispenser can be manually activated, but the force required todispense the fabric care composition is provided by another, non-manualmeans. Non-manually operated sprayers include, but are not limited to,powered sprayers, air aspirated sprayers, liquid aspirated sprayers,electrostatic sprayers, and nebulizer sprayers. The fabric carecomposition is placed into a spray dispenser in order to be distributedonto the fabric.

Powered sprayers include self contained powered pumps that pressurizethe aqueous fabric care composition and dispense it through a nozzle toproduce a spray of liquid droplets. Powered sprayers are attacheddirectly or remotely through the use of piping/tubing to a reservoir(such as a bottle) to hold the aqueous fabric care composition. Poweredsprayers can include, but are not limited to, centrifugal or positivedisplacement designs. It is preferred that the powered sprayer bepowered by a portable DC electrical current from either disposablebatteries (such as commercially available alkaline batteries) orrechargeable battery units (such as commercially available nickelcadmium battery units). Powered sprayers can also be powered by standardAC power supply available in most buildings. The discharge nozzle designcan be varied to create specific spray characteristics (such as spraydiameter and particle size). It is also possible to have multiple spraynozzles for different spray characteristics. The nozzle may or may notcontain an adjustable nozzle shroud that would allow the spraycharacteristics to be altered.

Nonlimiting examples of commercially available powered sprayers aredisclosed in U.S. Pat. No. 4,865,255, Luvisotto, issued Sep. 12, 1989which is incorporated herein by reference. Preferred powered sprayersare readily available from suppliers such as Solo, Newport News, Va.(e.g., Solo Spraystar™ rechargeable sprayer, listed as manual part #:U.S. Pat. No. 460,395) and Multi-sprayer Systems, Minneapolis, Minn.(e.g., model: Spray 1).

Air aspirated sprayers include the classification of sprayersgenerically known as “air brushes”. A stream of pressurized air draws upthe aqueous fabric care composition and dispenses it through a nozzle tocreate a spray of liquid. The fabric care composition can be suppliedvia separate piping/tubing or more commonly is contained in a jar towhich the aspirating sprayer is attached.

Nonlimiting examples of commercially available air aspirated sprayersappears in U.S. Pat. No. 1,536,352, Murray, issued Apr. 22, 1924 andU.S. Pat. No. 4,221,339, Yoshikawa, issues Sep. 9, 1980; all of saidreferences are incorporated herein by reference. Air aspirated sprayersare readily available from suppliers such as The Badger Air-Brush Co.,Franklin Park, Ill. (e.g., model #: 155) and Wilton Air Brush Equipment,Woodridge, Ill. (e.g., stock #: 415-4000, 415-4001, 415-4100).

Liquid aspirated sprayers are typical of the variety in widespread useto spray garden chemicals. The aqueous dewrinkling composition is drawninto a fluid stream by means of suction created by a Venturi effect. Thehigh turbulence serves to mix the aqueous fabric care composition withthe fluid stream (typically water) in order to provide a uniformmixture/concentration. It is possible with this method of delivery todispense the aqueous concentrated fabric care composition of the presentinvention and then dilute it to a selected concentration with thedelivery stream.

Liquid aspirated sprayers are readily available from suppliers such asChapin Manufacturing Works, Batavia, N.Y. (e.g., model #: 6006).

Electrostatic sprayers impart energy to the aqueous fabric carecomposition via a high electrical potential. This energy serves toatomize and charge the aqueous fabric care composition, creating a sprayof fine, charged particles. As the charged particles are carried awayfrom the sprayer, their common charge causes them to repel one another.This has two effects before the spray reaches the target. First, itexpands the total spray mist. This is especially important when sprayingto fairly distant, large areas. The second effect is maintenance oforiginal particle size. Because the particles repel one another, theyresist collecting together into large, heavier particles like unchargedparticles do. This lessens gravity's influence, and increases thecharged particle reaching the target. As the mass of negatively chargedparticles approach the target, they push electrons inside the targetinwardly, leaving all the exposed surfaces of the target with atemporary positive charge. The resulting attraction between theparticles and the target overrides the influences of gravity andinertia. As each particle deposits on the target, that spot on thetarget becomes neutralized and no longer attractive. Therefore, the nextfree particle is attracted to the spot immediately adjacent and thesequence continues until the entire surface of the target is covered.Hence, charged particles improve distribution and reduce drippage.

Nonlimiting examples of commercially available electrostatic sprayersappears in U.S. Pat. No. 5,222,664, Noakes, issued Jun. 29, 1993; U.S.Pat. No. 4,962,885, Coffee, issued Oct. 16, 1990; U.S. Pat. No.2,695,002, Miller, issued November 1954; U.S. Pat. No. 5,405,090,Greene, issued Apr. 11, 1995; U.S. Pat. No. 4,752,034, Kuhn, issued Jun.21, 1988; U.S. Pat. No. 2,989,241, Badger, issued June 1961; all of saidpatents are incorporated herein by reference. Electrostatic sprayers arereadily available from suppliers such as Tae In Tech Co, South Korea andSpectrum, Houston, Tex.

Nebulizer sprayers impart energy to the aqueous dewrinkling compositionvia ultrasonic energy supplied via a transducer. This energy results inthe aqueous fabric care composition to be atomized. Various types ofnebulizers include, but are not limited to, heated, ultrasonic, gas,venturi, and refillable nebulizers.

Nonlimiting examples of commercially available nebulizer sprayersappears in U.S. Pat. No. 3,901,443, Mitsui, issued Aug. 26, 1975; U.S.Pat. No. 2,847,248, Schmitt, issued August 1958; U.S. Pat. No.5,511,726, Greenspan, issued Apr. 30, 1996; all of said patents areincorporated herein by reference. Nebulizer sprayers are readilyavailable from suppliers such as A&D Engineering, Inc., Milpitas, Calif.(e.g., model A&D Un-231 ultrasonic handy nebulizer) and Amici, Inc.,Spring City, Pa. (model: swirler nebulizer).

The preferred article of manufacture herein comprises a non-manuallyoperated sprayer, such as a battery-powered sprayer, containing theaqueous fabric care composition. More preferably the article ofmanufacture comprises a combination of a non-manually operated sprayerand a separate container of the aqueous fabric care composition, to beadded to the sprayer before use and/or to be separated forfilling/refilling. The separate container can contain an usagecomposition, or a concentrated composition to be diluted before use,and/or to be used with a diluting sprayer, such as with a liquidaspirated sprayer, as described herein above.

Also, as described hereinbefore, the separate container should havestructure that mates with the rest of the sprayer to ensure a solid fitwithout leakage, even after motion, impact, etc. and when handled byinexperienced consumers. The sprayer desirably can also have anattachment system that is safe and preferably designed to allow for theliquid container to be replaced by another container that is filled.E.g., the fluid reservoir can be replaced by a filled container. Thiscan minimize problems with filling, including minimizing leakage, if theproper mating and sealing means are present on both the sprayer and thecontainer. Desirably, the sprayer can contain a shroud to ensure properalignment and/or to permit the use of thinner walls on the replacementcontainer. This minimizes the amount of material to be recycled and/ordiscarded. The package sealing or mating system can be a threadedclosure (sprayer) which replaces the existing closure on the filled andthreaded container. A gasket is desirably added to provide additionalseal security and minimize leakage. The gasket can be broken by actionof the sprayer closure. These threaded sealing systems can be based onindustry standards. However, it is highly desirable to use a threadedsealing system that has non-standard dimensions to ensure that theproper sprayer/bottle combination is always used. This helps prevent theuse of fluids that are toxic, which could then be dispensed when thesprayer is used for its intended purpose.

An alternative sealing system can be based on one or more interlockinglugs and channels. Such systems are commonly referred to as “bayonet”systems. Such systems can be made in a variety of configurations, thusbetter ensuring that the proper replacement fluid is used. Forconvenience, the locking system can also be one that enables theprovision of a “child-proof” cap on the refill bottle. This“lock-and-key” type of system thus provides highly desirable safetyfeatures. There are a variety of ways to design such lock and keysealing systems.

Care must be taken, however, to prevent the system from making thefilling and sealing operation too difficult. If desired, the lock andkey can be integral to the sealing mechanism. However, for the purposeof ensuring that the correct recharge or refill is used, theinterlocking pieces can be separate from the sealing system. E.g., theshroud and the container could be designed for compatibility. In thisway, the unique design of the container alone could provide therequisite assurance that the proper recharge/refill is used.

Examples of threaded closures and bayonet systems can be found in U.S.Pat. No. 4,781,311, Nov. 1, 1988 (Angular Positioned Trigger Sprayerwith Selective Snap-Screw Container Connection, Clorox), U.S. Pat. No.5,560,505, Oct. 1, 1996 (Container and Stopper Assembly Locked Togetherby Relative Rotation and Use Thereof, Cebal SA), and U.S. Pat. No.5,725,132, Mar. 10, 1998 (Dispenser with Snap-Fit Container Connection,Centico International). All of said patents are incorporated herein byreference.

The present invention also relates to an article of manufacturecomprising a fabric care composition for use in spraying and/or mistingan entire garment in a manner such that excessive amounts of thefabric/garment care composition are prevented from being released to theopen environment, provided in association with instructions for use toensure that the consumer applies at least an effective amount of fabriccare polysaccharied with globular structure and/or fabric carecomposition, to provide the desired garment care benefit, typically fromabout 0.001% to about 0.5%, preferably from about 0.01% to about 0.2%,more preferably from about 0.02% to about 0.05%, by weight of thegarment.

Other fabric care compositions of the present invention for use to treatfabrics in different steps of the laundry process, e.g., pre-wash, washcycle, rinse cycle, and drying cycle, can be packaged in associationwith instructions for how to use the composition to treat fabricscorrectly, in order to obtain the desirable fabric care results, viz,wrinkle removal and/or reduction, wrinkle resistance, fiberstrengthening/anti-wear, fabric wear reduction, fabric shrinkageprevention and/or reduction, fabric pill prevention and/or reduction,shrinkage prevention and/or reduction, fabric color maintenance, fabriccolor fading reduction, soiling prevention and/or reduction, and/orfabric shape retention, and mixtures thereof.

III. Method of Use

The fabric care composition, which contains a fabric care polysaccharidewith globular structure, and optionally, e.g., adjunct fabric careoligosaccharides, perfume, fiber lubricant, adjunct fabric shaperetention polymer, lithium salt, hydrophilic plasticizer, odor controlagent including cyclodextrin, antimicrobial actives and/or preservative,surfactant, enzyme, antioxidant, metal chelating agent includingaminocarboxylate chelating agent, antistatic agent, insect and mothrepelling agent, fabric softener active, electrolyte, chlorinescavenging agent, dye transfer inhibiting agent, dye fixing agent, phasestabilizer, colorant, brightener, soil release agent, builder,dispersant, suds suppressor, etc., and mixtures thereof, can be used bydistributing, e.g., by placing, an effective amount of the aqueoussolution onto the fabric surface or fabric article to be treated.Distribution can be achieved by using a spray device, a roller, a pad,etc., preferably a spray dispenser. For wrinkle control, for wrinkleremoval, an effective amount means an amount sufficient to remove ornoticeably reduce the appearance of wrinkles on fabric. Preferably, theamount of fabric care solution is not so much as to saturate or create apool of liquid on said article or surface and so that when dry there isno visual deposit readily discernible.

The compositions and articles of the present invention which contain afabric care polysaccharide with globular structure can be used to treatfabrics, garments, and the like, to provide at least one of thefollowing fabric care benefits: wrinkle removal, wrinkle reduction,wrinkle resistance, fabric wear reduction, fabric wear resistance,fabric pilling reduction, fabric color maintenance, fabric color fadingreduction, fabric color restoration, fabric soiling reduction, fabricshape retention, and/or fabric shrinkage reduction.

An effective amount of the liquid composition of the present inventionis preferably sprayed onto fabric and/or fabric articles include, butare not limited to, clothes, curtains, drapes, upholstered furniture,carpeting, bed linens, bath linens, tablecloths, sleeping bags, tents,car interiors, etc. When the composition is sprayed onto fabric, aneffective amount should be deposited onto the fabric, with the fabricbecoming damp or totally saturated with the composition, typically fromabout 5% to about 150%, preferably from about 10% to about 100%, morepreferably from about 20% to about 75%, by weight of the fabric. Thetreated fabric typically has from about 0.005% to about 4%, preferablyfrom about 0.01% to about 2%, more preferably from about 0.05% to about1%, by weight of the fabric of said fabric care polysaccharide withglobular structure. For wrinkle removal, once an effective amount of thecomposition is sprayed onto the fabric, the fabric is optionally, butpreferably stretched. The fabric is typically stretched perpendicular tothe wrinkle. The fabric can also be smoothed by hand after it has beensprayed. The smoothing movement works particularly well on areas ofclothing that have an interface sewn into them, or on the hems ofclothing. Once the fabric has been sprayed and optionally, butpreferably, stretched, it is hung until dry. It is preferable that thetreatment is performed in accordance with the instructions for use, toensure that the consumer knows what benefits can be achieved, and howbest to obtain these benefits.

The spraying means should be capable of providing droplets with a weightaverage diameter of from about 5 μm to about 250 μm, preferably fromabout 8 μm to about 120 μm, more preferably from about 10 μm to about 80μm. When the compositions are applied in the form of the very smallparticles (droplets), the distribution is further improved and overallperformance is also improved. The presence of the optional surfactantpromotes spreading of the solution and the optional antimicrobial activeprovides improved odor control as well as antimicrobial action, byminimizing the formation of odors.

The fabric care composition can also be applied to fabric via a dippingand/or soaking process followed by a drying step. The application can bedone industrially by large scale processes on textiles and/or finishedgarments and clothings, or in consumer's home by the use of commercialproduct.

The present invention also comprises a method of using concentratedliquid or solid fabric care compositions, which are diluted to formcompositions with the usage concentrations, as given hereinabove, foruse in the “usage conditions”. Concentrated compositions comprise ahigher level of fabric care polysaccharide with globular structure,typically from about 1% to about 99%, preferably from about 2% to about65%, more preferably from about 3% to about 25%, by weight of theconcentrated fabric care composition. Concentrated compositions are usedin order to provide a less expensive product. The concentrated productis preferably diluted with about 50% to about 10,000%, more preferablyfrom about 50% to about 8,000%, and even more preferably from about 50%to about 5,000%, by weight of the composition, of water.

The compositions of the present invention can also be used as ironingaids. An effective amount of the composition can be sprayed onto fabricand the fabric is ironed at the normal temperature at which it should beironed. The fabric can either be sprayed with an effective amount of thecomposition, allowed to dry and then ironed, or sprayed and ironedimmediately.

In a still further aspect of the invention, the composition can besprayed and/or misted onto fabrics and/or entire garments in need ofde-wrinkling and/or other fabric care benefits in a manner such thatexcessive amounts of the fabric/garment care composition are preventedfrom being released to the open environment, provided in associationwith instructions for use to ensure that the consumer applies at leastan effective amount of fabric care polysaccharide with globularstructure and/or fabric care composition, to provide the desired garmentcare benefit. Any spraying mechanism and/or misting mechanism can beused to apply the fabric care composition to fabrics and/or garments. Apreferred distribution of the garment care composition is achieved byusing a fog form. The mean particulate diameter size of the fabric carecomposition fog is preferably from about 3 microns to about 50 microns,more preferably from about 5 microns to about 30 microns, and mostpreferably from about 10 microns to about 20 microns.

Another aspect of the present invention is the method of using anaqueous or solid, preferably powder, fabric care composition fortreating fabric in the rinse step, comprising an effective amount ofsaid fabric care polysaccharide with globular structure, and optionally,adjunct fabric care oligosaccharides, fabric softener actives, perfume,electrolytes, chlorine scavenging agents, dye transfer inhibitingagents, dye fixing agents, phase stabilizers, chemical stabilizersincluding antioxidants, silicones, antimicrobial actives and/orpreservatives, chelating agents, aminocarboxylate chelating agents,colorants, enzymes, brighteners, soil release agents, or mixturesthereof. The rinse water should contain typically from about 0.0005% toabout 1%, preferably from about 0.0008% to about 0.1%, more preferablyfrom about 0.001% to about 0.02% of the fabric care polysaccharides.

The present invention also relates to a method of using an aqueous orsolid, preferably powder or granular, fabric care composition to treatthe fabrics in the wash cycle, said compositions comprise fabric carepolysaccharide with globular structure, and optionally, adjunct fabriccare oligosaccharides, surfactants, builders, perfume, chlorinescavenging agents, dye transfer inhibiting agents, dye fixing agents,dispersants, detergent enzymes, heavy metal chelating agents, sudssuppressors, fabric softener actives, chemical stabilizers includingantioxidants, silicones, antimicrobial actives and/or preservatives,soil suspending agents, soil release agents, optical brighteners,colorants, and the like, or mixtures thereof. Depending on the selectionof optional ingredients, such as the level and type of surfactants, thewash-added fabric care composition can be used as a wash additivecomposition (when the surfactant level is low) or as a laundry detergentwhich also has additional fabric care benefits. It is preferable thatthe treatment is performed in accordance with the instructions for use,to ensure that the consumer knows what benefits can be achieved, and howbest to obtain these benefits.

The present invention also relates to a method for treating fabric inthe drying step, comprising an effective amount of said fabric carepolysaccharide with globular structure, and optionally, adjunct fabriccare oligosaccharides, fabric softener actives, distributing agent,perfume, fiber lubricants, fabric shape retention polymers, lithiumsalts, phase stabilizers, chlorine scavenging agents, dye transferinhibiting agents, dye fixing agents, chemical stabilizers includingantioxidants, silicones, antimicrobial actives and/or preservatives,heavy metal chelating agents, aminocarboxylate chelating agents,enzymes, brighteners, soil release agents, and mixtures thereof. Thefabric care composition can take a variety of physical forms includingliquid, foams, gel and solid forms such as solid particulate forms. Apreferred method comprises the treatment of fabric with a dryer-addedfabric care composition in combination with a dispensing means such as aflexible substrate which effectively releases the fabric carecomposition in an automatic tumble clothes dryer. Such dispensing meanscan be designed for single usage or for multiple uses. Preferably thecomposition is applied onto a sheet substrate to form a dryer sheetproduct. Another preferred method comprises the treatment of fabricswith a fabric care composition dispensed from a a sprayer at thebeginning and/or during the drying cycle. It is preferable that thetreatment is performed in accordance with the instructions for use, toensure that the consumer knows what benefits can be achieved, and howbest to obtain these benefits.

The present invention also relates to a fabric care method of dippingand/or soaking fabrics before the fabrics is laundered, with a pre-washfabric care composition containing an effective amount of fabric carepolysaccharide with globular structure, and optionally, adjunct fabriccare oligosaccharides, surfactants, builders, perfume, chlorinescavenging agents, dye transfer inhibiting agents, dye fixing agents,dispersants, detergent enzymes, heavy metal chelating agents, fabricsoftener actives, chemical stabilizers including antioxidants,silicones, antimicrobial actives and/or preservatives, soil suspendingagents, soil release agents, optical brighteners, colorants, and thelike, or mixtures thereof. It is preferable that the treatment isperformed in accordance with the instructions for use, to ensure thatthe consumer knows what benefits can be achieved, and how best to obtainthese benefits.

All percentages, ratios, and parts herein, in the Specification,Examples, and claims are by weight and are the normal approximationsunless otherwise stated.

The following are non-limiting examples of the instant composition.

Illustrative examples of fabric care polysaccharides with globularstructure and with 1,3-β-linked backbone to be used in the followingExamples are as follows:

-   Arabinogalactan A: arabinogalactan fraction that has the average    molecular weight of from about 16,000 to about 20,000.-   Arabinogalactan B: arabinogalactan fraction that has the average    molecular weight of about 100,000.-   Arabinogalactan C: arabinogalactan fraction that has the average    molecular weight of from about 10,000 to about 150,000.

Illustrative examples of adjunct fabric care oligosaccharide mixtures tobe used in the following Examples are as follows:

Isomaltooligosaccharide (IMO) Mixture A Trisaccharides (maltotriose,panose, isomaltotriose) 40% Disaccharides (maltose, isomaltose) 25%Monosaccharide (glucose) 20% Higher branched sugars (4 < DP < 10) 15%Isomaltooligosaccharide (IMO) Mixture B Trisaccharides (maltotriose,panose, isomaltotriose) 25% Disaccharides (maltose, isomaltose) 56%Monosaccharide (glucose) 16% Higher branched sugars (DP > 4 < 10)  4%Branched Oligosaccharide Mixture C Tetrasaccharides (stachyose) 32%Trisaccharides (raffinose)  6% Disaccharides (sucrose, trehalose) 39%Monosaccharide (glucose, fructose)  1% Higher branched sugars (4 < DP <10) 0–5% Isomaltooligosaccharide (IMO) Mixture D Trisaccharides(maltotriose, panose, isomaltotriose) 62% Disaccharides (maltose,isomaltose) 13% Monosaccharide (glucose)  1% Higher branched sugars (4 <DP < 10) 24%

Illustrative examples of perfume compositions to be used in thefollowing Examples are as follows:

Perfume Ingredients Wt. % Volatile Perfume A alpha-Pinene 5.0 DihydroMyrcenol 10.0 Eucalyptol 10.0 Eugenol 5.0 Flor Acetate 10.0 Lemon Oil10.0 Linalool 10.0 Linalyl Acetate 5.0 Orange Terpenes 15.0 Phenyl EthylAlcohol 20.0 Total 100.0 Substantive Perfume B Benzyl Salicylate 10.0Coumarin 5.0 Ethyl Vanillin 2.0 Ethylene Brassylate 10.0 Galaxolide 15.0Hexyl Cinnamic Aldehyde 20.0 Gamma Methyl Ionone 10.0 Lilial 15.0 MethylDihydrojasmonate 5.0 Patchouli 5.0 Tonalid 3.0 Total 100.0 HydrophilicPerfume C Benzophenone 0.3 Benzyl acetate 4.0 Benzyl propionate 1.0 betagamma Hexenol 0.3 Cetalox 0.1 cis 3 Hexenyl acetate 0.5 cis Jasmone 0.3cis-3-Hexenyl salicylate 0.5 Citral 0.5 Citronellal nitrile 0.7Citronellol 1.5 Coumarin 3.0 Cyclal C 0.3 Cyclo galbanate 0.4 betaDamascone 0.1 Dihydro myrcenol 2.0 Ebanol 0.5 Flor acetate 4.5Florhydral 1.0 Fructone 4.0 Frutene 5.0 Geranyl nitrile 0.4 Heliotropin1.5 Hydroxycitronellal 3.0 Linalool 2.5 Linalyl acetate 0.5 Methyldihydro jasmonate 5.0 Methyl heptine carbonate 0.3 Methyl iso butenyltetrahydro pyran 0.2 Methyl phenyl carbinyl acetate 0.5 Nonalactone 1.5P. T. Bucinal 2.0 para Hydroxy phenylbutanone 1.3 Phenoxy ethanol 30.0Phenyl ethyl acetate 0.8 Phenyl ethyl alcohol 15.0 Prenyl acetate 1.5Terpineol 2.0 Verdox 1.0 Vanillin 0.5 Total 100.0The following non-limiting fabric care compositions are prepared bymixing and dissolving the ingredients into clear or translucentsolutions, in accord with the present invention:

EXAMPLE IA

Ia Ib Ic Id Ie If Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabino- 0.5 — — 1 — — galactan A Arabino- — 0.3 — — 0.5 — galactan BArabino- — — 0.5 — — 0.5 galactan C Volatile — — — 0.1 — — Perfume ASubstantive — — — — 0.03 — Perfume B Hydrophilic — — — — — 0.05 PerfumeC Polysorbate — — — 0.2 0.1 — 60⁽¹⁾ Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water ⁽¹⁾A mixture ofstearate esters of sorbitol and sorbitol anhydride, consistingpredominantly of the monoester, condensed with about 20 moles ofethylene oxide.

EXAMPLE IB

Ig Ih Ii Ij Ik Il Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Quaternized 0.5 — — 1 — — Arabino- galactan A⁽²⁾ Curdlan⁽³⁾ — 0.3 — —0.3 — Dextran⁽⁴⁾ — — 0.6 — — 0.5 Volatile — — — 0.1 — — Perfume ASubstantive — — — — 0.03 — Perfume B Hydrophilic — — — — — 0.05 PerfumeC Polysorbate 60 — — — 0.2 0.1 — Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water ⁽²⁾Quaternizedarabinogalactan containing about 1.5% by weight of3-chloro-2-hydroxypropyltrimethyl ammonium chloride. ⁽³⁾Averagemolecular weight of about 72,000. ⁽⁴⁾Average molecular weight of about40,000.

EXAMPLE II

IIa IIb IIc IId IIe IIf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabino- 2 0.3 0.5 0.5 1 — galactan A Arabino- — — — — — 1 galactan BOligo- — 0.3 — — — — saccharide Mixture A Oligo- — — 0.5 — — —saccharide Mixture B Oligo- — — — 0.3 — — saccharide Mixture C Oligo- —— — — 0.5 0.5 saccharide Mixture D Volatile 0.1 — — 0.1 — — Perfume ASubstantive 0.2 — — — 0.03 — Perfume B Hydrophilic — —  0.05 — — 0.05Perfume C Polysorbate 60 0.3 — — 0.2 0.1 — Kathon CG 3 ppm 3 ppm 3 ppm 3ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. WaterFabric care compositions of Examples I and II are usage compositionsfor, e.g., spraying, soaking, dipping of fabrics, and/or pre-washtreatments.

EXAMPLE III

IIIa IIIb IIIc IIId IIIe IIIf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. %Wt. % Arabino- 15 — — 5 — — galactan A Arabino- — 25 — — 15 — galactan BArabino- — — 5 — — 25 galactan C Perfume A — — — — 1 — Perfume B — — —0.3 — — Perfume C — — — — — 1.5 Polysorbate 60 — — — 0.5 1.5 1 Kathon CG5 ppm 10 ppm 5 ppm 5 ppm 5 ppm 5 ppm Deionized Bal. Bal. Bal. Bal. Bal.Bal. Water

EXAMPLE IV

IVa IVb IVc IVd IVe IVf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabino- 1.5 — 20 3 10 — galactan A Arabino- — 2 — — — 2 galactan BOligo- — — — 2 — saccharide Mixture A Oligo- — — — — 5 — saccharideMixture B Oligo- — —  5 — — — saccharide Mixture C Oligo- 3.5 8 — — — 20saccharide Mixture D Perfume A — — — — 1 — Perfume B — — — 0.3 — —Perfume C — — — — — 1.5 Polysorbate 60 — — — 0.5 1.5 1 Kathon CG 5 ppm 5ppm 5 ppm 5 ppm 5 ppm 5 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.WaterConcentrated compositions of Examples III and IV are diluted with waterto obtain usage compositions for, e.g., spraying, soaking and/or dippingfabric articles. They can also be used undiluted to treat fabric as washadditive and/or rinse additive compositions.

EXAMPLE V

Va Vb Vc Vd Ve Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % ArabinogalactanA 1 — — — 1.5 Arabinogalactan B — 0.5 — 1 — Arabinogalactan C — — 0.5 —— LiBr 3 — — 2 2 Silicone Emulsion A⁽⁵⁾ — 1.5 — — 2.0 D5 VolatileSilicone — — 0.5 0.5 — Perfume A — — — — 0.03 Perfume B — — — 0.05 —Perfume C 0.03 — — — — Polysorbate 60 — — — 0.1 0.05 Silwet L-7602 — — —0.5 — Silwet L-7622 — — — — 0.3 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppmDeionized Water Bal. Bal. Bal. Bal. Bal. ⁽⁵⁾DC-2-5932 siliconemicroemulsion (25% active) from Dow Corning, with a particle size ofabout 24 nm, a cationic surfactant system, and a silicone with aninternal phase viscosity of about 1,200 cps.

EXAMPLE VIA

VIa VIb VIc VId VIe Ingredients Wt. % Wt. % Wt. % Wt. % Wt. %Arabinogalactan A 0.45 0.5 0.7 0.8 — Arabinogalactan B — — — — 0.2Oligosaccharide 0.05 — — — — Mixture A Oligosaccharide — 1 — — — MixtureB Oligosaccharide — — 0.3 — — Mixture C Oligosaccharide — — — 1.2 0.8Mixture D LiBr 3 — — 2 2 Silicone Emulsion A⁽⁵⁾ — 1.5 — — 2.0 D5Volatile Silicone — — 0.5 0.5 — Perfume A — — — — 0.03 Perfume B — — —0.05 — Perfume C 0.03 — — — — Polysorbate 60 — — — 0.1 0.05 SilwetL-7602 — — — 0.5 — Silwet L-7622 — — — — 0.3 Kathon CG 3 ppm 3 ppm 3 ppm3 ppm 3 ppm Deionized Water Bal. Bal. Bal. Bal. Bal. ⁽⁵⁾DC-2-5932silicone microemulsion (25% active) from Dow Corning, with a particlesize of about 24 nm, a cationic surfactant system, and a silicone withan internal phase viscosity of about 1,200 cps.

EXAMPLE VIB

VIf VIg VIh VIi VIj Ingredients Wt. % Wt. % Wt. % Wt. % Wt. %Quaternized 0.75 — — — 0.2 Arabinogalactan A Curdlan — 0.3 — — — Dextran— — 0.7 0.8 — Oligosaccharide 0.05 — — — — Mixture A Oligosaccharide — 1— — — Mixture B Oligosaccharide — — 0.3 — — Mixture C Oligosaccharide —— — 1.2 0.8 Mixture D LiBr 3 — — 2 2 Silicone Emulsion A⁽⁵⁾ — 1.5 — —2.0 D5 Volatile Silicone — — 0.5 0.5 — Perfume A — — — — 0.03 Perfume B— — — 0.05 — Perfume C 0.03 — — — — Polysorbate 60 — — — 0.1 0.05 SilwetL-7602 — — — 0.5 — Silwet L-7622 — — — — 0.3 Kathon CG 3 ppm 3 ppm 3 ppm3 ppm 3 ppm Deionized Water Bal. Bal. Bal. Bal. Bal.

EXAMPLE VII

VIIa VIIb VIIc VIId VIIe VIIf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. %Wt. % Arabino- 0.7 — — 1 0.5 — galactan A Arabino- — 0.5 — — — 0.5galactan B Arabino- — — 0.5 — — — galactan C Copolymer A⁽⁶⁾ 0.4 — — — —0.5 Copolymer B⁽⁷⁾ — 0.5 — 0.3 — — Copolymer C⁽⁸⁾ — — 0.6 — 0.5 — LiBr —— — 3 — 2 Silicone — — — — 1.5 — Emulsion A⁽⁵⁾ D5 Volatile — — — — — 0.5Silicone Perfume A  0.06 — — — — 0.07 Perfume B —  0.03 — 0.03 — —Perfume C — —  0.04 — 0.03 — Polysorbate 60 0.1 0.1  0.03 0.1 0.1 0.1Silwet L-7600 — — — 0.5 — — Silwet L-7602 — — — — — 0.7 Kathon CG 3 ppm3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.Water ⁽⁵⁾DC-2-5932 silicone microemulsion (25% active) from Dow Corning,with a particle size of about 24 nm, a cationic surfactant system, and asilicone with an internal phase viscosity of about 1,200 cps. ⁽⁶⁾Acrylicacid/tert-butyl acrylate copolymer, with an approximate acrylicacid/tert-butyl acrylate weight ratio of about 25/75 and an averagemolecular weight of from about 70,000 to about 100,000. ⁽⁷⁾Acrylicacid/tert-butyl acrylate copolymer, with an approximate acrylicacid/tert-butyl acrylate weight ratio of about 35/65 and an averagemolecular weight of from about 60,000 to about 90,000. ⁽⁸⁾Acrylicacid/tert-butyl acrylate copolymer, with an approximate acrylicacid/tert-butyl acrylate weight ratio of about 20/80 and an averagemolecular weight of from about 80,000 to about 110,000.

EXAMPLE VIII

VIIIa VIIIb VIIIc VIIId VIIIVe VIIIf Ingredients Wt. % Wt. % Wt. % Wt. %Wt. % Wt. % Arabino- 0.9 — — 0.5  0.75 0.7 galactan A Arabino- — 0.5 — —— — galactan B Arabino- — — 0.5 — — — galactan C Oligo- 0.3 — — —  0.25— saccharide Mixture A Oligo- — 1 — — — — saccharide Mixture B Oligo- —— 0.5 — — — saccharide Mixture C Oligo- — — — 1.5 — 1 saccharide MixtureD Copolymer A⁽⁶⁾ 0.4 — — — — 0.5 Copolymer B⁽⁷⁾ — 0.5 — 0.3 — —Copolymer C⁽⁸⁾ — — 0.6 — 0.5 — LiBr — — — 3 — 2 Silicone — — — — 1.5 —Emulsion A⁽⁵⁾ D5 Volatile — — — — — 0.5 Silicone Perfume A  0.06 — — — —0.07 Perfume B — 0.03 — 0.03 — — Perfume C — —  0.04 —  0.03 —Polysorbate 60 0.1 0.1  0.03 0.1 0.1 0.1 Silwet L-7600 — — — 0.5 — —Silwet L-7602 — — — — — 0.7 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. Water

EXAMPLE IX

IXa IXb IXc IXd IXe IXf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabinogalactan A 0.7 — — — 7 1 Arabinogalactan B — 0.5 — 0.5 — —Arabinogalactan C — — 0.5 — — — Copolymer D⁽⁹⁾ 0.4 — — — 2 0.25Copolymer E⁽¹⁰⁾ — 0.5 — — — 0.25 Copolymer F⁽¹¹⁾ — — 0.4 — — — CopolymerG⁽¹²⁾ — — — 0.5 — — D5 Volatile Silicone — 0.25 — — — — PDMS 10,000 cst— — — 0.3 — — Silicone Emulsion B⁽¹³⁾ — — 1 — 2 — Perfume A 0.06 — — — —0.07 Perfume B — 0.03 — 0.03 — — Perfume C — — 0.04 — 0.5 — Polysorbate60 0.1 0.1 — 0.1 0.5 0.1 Neodol 23-3 — 0.25 — 0.2 — — Neodol 25-3 — —0.3 — 0.3 0.25 Silwet L-77 — 0.7 — 1 — — Silwet L-7604 — — 0.5 — — 0.7Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 5 ppm 3 ppm Deionized Water Bal. Bal.Bal. Bal. Bal. Bal. ⁽⁹⁾Acrylic acid/tert-butyl acrylate copolymer, withan approximate acrylic acid/tert-butyl acrylate weight ratio of about23/77 and an average molecular weight of about 82,000.⁽¹⁰⁾Silicone-containing copolymer having t-butyl acrylate/acrylicacid/(polydimethylsiloxane macromer, 10,000 approximate molecularweight) monomer at an approximate 63/20/17 weight ratio, and of anaverage molecular weight of about 130,000. ⁽¹¹⁾Silicone-containingcopolymer having t-butylacrylate/acrylic acid/(polydimethylsiloxanemacromer, 10,000 approximate molecular weight) monomer at an approximate65/25/10 weight ratio, and of average molecular weight of about 200,000.⁽¹²⁾Silicone-containing copolymer having (N,N,N-trimethylammonioethylmethacrylate chloride)/N,N-dimethylacrylamide/(PDMS macromer - 15,000approximate molecular weight) at an approximate 40/40/20 weight ratio,and of average molecular weight of about 150,000. ⁽¹³⁾DC-1550 siliconemicroemulsion (25% active) from Dow Corning, with a particle size ofabout 50 nm, an anionic/nonionic surfactant system, and a silicone withan internal phase viscosity of about 100,000 cps. The composition ofExample IXe is a concentrated composition, to be diluted for use.

EXAMPLE X

Xa Xb Xc Xd Xe Xf Ingredients Wt. % Wt. % Wt. % Wt. % Wt. % Wt. %Arabino- — 0.5 0.8 — 6 2 galactan A Arabino- 0.7 — — — — — galactan BArabino- — — — 0.35 — — galactan C Oligo- 0.7 — — — — — saccharideMixture A Oligo- — 1 — 0.85 — — saccharide Mixture B Oligo- — — 0.2 — —— saccharide Mixture C Oligo- — — — — 5 0.5 saccharide Mixture DCopolymer 0.4 — — — 2 0.25 D⁽⁹⁾ Copolymer — 0.5 — — — 0.25 E⁽¹⁰⁾Copolymer — — 0.4 — — — F⁽¹¹⁾ Copolymer — — — 0.5 — — G⁽¹²⁾ D5 Volatile— 0.25 — — — — Silicone PDMS — — — 0.3 — — 10,000 cst Silicone — — 1 — 2— Emulsion B⁽¹³⁾ Perfume A  0.06 — — — — 0.07 Perfume B — 0.03 — 0.03 —— Perfume C — — 0.04 — 0.5 — Polysorbate 60 0.1 0.1 — 0.1 0.5 0.1 Neodol23-3 — 0.25 — 0.2 — — Neodol 25-3 — — 0.3 — 0.3 0.25 Silwet L-77 — 0.7 —1 — — Silwet L-7604 — — 0.5 — — 0.7 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 10ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. WaterThe composition of Example Xe is a concentrated composition, to bediluted for use.

EXAMPLE XI

XIa XIb XIc XId XIe XIf Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Arabino- 0.8 — — 1 — 1.5 galactan A Arabino- — 0.5 — — 0.7 — galactan BArabino- — — 0.5 — — — galactan C HPBCD⁽¹⁴⁾ 1 — 0.5 — 0.5 — RAMEB⁽¹⁵⁾ —1 — — — — HPACD⁽¹⁶⁾ — — 0.5 — — — α-Cyclodextrin — — — — 0.5 0.5β-Cyclodextrin — — — 0.5 — 0.5 ZnCl₂ — 1.0 — 1.0 — 1 Silwet L-7657 — — ——  0.05 — Perfume C 0.1 0.07  0.05 — 0.1 0.05 Propylene 0.06 —  0.05 — 0.03 — glycol Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm HCl — to —to — to pH 4.5 pH 5 pH 4.5 Distilled water Bal. Bal. Bal. Bal. Bal. Bal.⁽¹⁴⁾Hydroxypropyl beta-cyclodextrin. ⁽¹⁵⁾Randomly methylatedbeta-cyclodextrin. ⁽¹⁶⁾Hydroxypropyl alpha-cyclodextrin.

EXAMPLE XII

XIIa XIIb XIIc XIId XIIe XIIf Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Arabino- 0.6 0.6 1 0.1 — — galactan A Arabino- — — — — 0.5 — galactan BArabino- — — — — — 0.3 galactan C Oligo- 0.9 — — — — — saccharideMixture A Oligo- — 0.4 — — 0.7 0.7 saccharide Mixture B Oligo- — — 0.5 —— — saccharide Mixture C Oligo- 0.9 saccharide Mixture D HPBCD⁽¹⁴⁾ 1 —0.5 — 0.5 — RAMEB⁽¹⁵⁾ — 1 — — — — HPACD⁽¹⁶⁾ — — 0.5 — — — α-Cyclodextrin— — — — 0.5 0.5 β-Cyclodextrin — — — 0.5 — 0.5 ZnCl₂ — 1.0 — 1.0 — 1Silwet L-7657 — — — —  0.05 — Perfume C 0.1 0.07 0.05 — 0.1 0.05Propylene 0.06 — 0.05 —  0.03 — glycol Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm3 ppm 3 ppm HCl — to — to — to pH 4.5 pH 5 pH 4.5 Distilled water Bal.Bal. Bal. Bal. Bal. Bal.

EXAMPLE XIII

XIIIa XIIIb XIIIc XIIId XIIIe XIIIf Ingredients Wt % Wt % Wt % Wt % Wt %Wt % Arabino- 0.7 — — 0.5 1 1 galactan A Arabino- — 0.5 — — — — galactanB Arabino- — — 1 — — — galactan C HPBCD 1.0 — — — — — RAMEB — 1.0 — — —— Silwet L-7604 0.3 0.2 0.2 — — 0.1 Chlorhexidine  0.01 — — — — 0.005Barquat — — 0.03 — — — 4250⁽¹⁷⁾ Bardac — — —  0.03 0.03 — 2050⁽¹⁸⁾Perfume C  0.08  0.08 0.05  0.05 — — HCl to — — — — — pH 4 Kathon CG 3ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal. Bal. Bal.Bal. Bal. ⁽¹⁷⁾Benzalkonium chloride, 50% solution. ⁽¹⁸⁾Dioctyl dimethylammonium chloride, 50% solution.

EXAMPLE XIVA

XIVa XIVb XIVc XIVd XIVe XIVf Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Arabino- 1 1 0.3 0.9 — — galactan A Arabino- — — — — 0.5 — galactan BArabino- — — — — — 0.2 galactan C Oligo- 0.7 — — — — — saccharideMixture A Oligo- — 0.5 — — 0.5 — saccharide Mixture B Oligo- — — 1.2 — —— saccharide Mixture C Oligo- — — — 0.6 — 1.8 saccharide Mixture D HPBCD1.0 — — — — — RAMEB — 1.0 — — — — Silwet L-7604 0.3 0.2 0.2 — — 0.1Chlorhexidine 0.01 — — — — 0.005 Barquat — —  0.03 — — — 4250⁽¹⁷⁾ Bardac— — —  0.03  0.03 — 2050⁽¹⁸⁾ Perfume C 0.08 0.08  0.05  0.05 — — HCl to— — — — — pH 4 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilledwater Bal. Bal. Bal. Bal. Bal. Bal.

EXAMPLE XIVB

XIVg XIVh XIVi XIVj XIVk XIVl Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Quaternized 0.5 — — 0.6 — — Arabino- galactan A Curdlan — 0.3 — — 0.2 —Dextran — — 0.3 — — 0.2 Oligo- 0.5 — — — — — saccharide Mixture A Oligo-— 0.5 — — 0.7 — saccharide Mixture B Oligo- — — 1.2 — — — saccharideMixture C Oligo- — — — 0.6 — 1.8 saccharide Mixture D HPBCD 1.0 — — — —— RAMEB — 1.0 — — — — Silwet L-7604 0.3 0.2 0.2 — — 0.1 Chlorhexidine 0.01 — — — — 0.005 Barquat 4250 — —  0.03 — — — Bardac 2050 — — —  0.03 0.03 — Perfume C  0.08  0.08  0.05  0.05 — — HCl to — — — — — pH 4Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Distilled water Bal. Bal.Bal. Bal. Bal. Bal.

The compositions of Examples I to XIV (diluted when appropriate) aresprayed onto clothing using, e.g., the TS-800 sprayer from Calmar, andallowed to evaporate off of the clothing.

The compositions of Examples I to XIV (diluted when appropriate) aresprayed onto clothing, using a blue inserted Guala® trigger sprayer,available from Berry Plastics Corp. and a cylindrical Euromist II® pumpsprayer available from Seaquest Dispensing, respectively, and allowed toevaporate off of the clothing.

The compositions of Examples I to XIV (diluted when appropriate)contained in rechargeable battery-operated Solo Spraystar sprayers aresprayed onto large surfaces of fabric, such as several pieces ofclothing, and allowed to evaporate off of these surfaces.

The compositions of Examples I to XIV (diluted when appropriate) areused for soaking or dipping of fabrics which are then optionally wrungor squeezed to remove excess liquid and subsequently dried.

Following are Examples for rinse-added fabric care compositions inaccordance with the present invention:

EXAMPLE XV

XVa XVb XVc XVd XVe Ingredients Wt % Wt % Wt % Wt. % Wt %Arabinogalactan A 8 — — 20 — Arabinogalactan B — 3 — — 15Arabinogalactan C — — 5 — — Fabric softener A⁽¹⁹⁾ 4.5 — — — — Fabricsoftener B⁽²⁰⁾ — 24 — — — Fabric softener C⁽²¹⁾ — — 26 — — Fabricsoftener D⁽²²⁾ — — — 28 28 Fabric softener E⁽²³⁾ 3.4 — — — —1,2-Hexanediol — — 18 — — 2-Ethyl-1,3-hexane- — — — 6 — diol Neodol 91-8— — — 5 3 Pluronic L-35 — — — 1 Hexylene glycol — — — — 3 Hexyleneglycol — — — 2.5 2.5 (from softener active) Ethanol (from soft- — 4.24.6 2.3 2.3 ener active) Perfume B 0.3 1.3 1.3 2 1.2 Tenox 6 antioxidant0.02 0.04 0.04 0.04 0.04 CaCl₂ 0.05 0.4 0.5 — 2 MgCl₂ — — — 1.6 — HCl topH 6 to pH 3.5 to pH 3.5 to pH 3 to pH 3 Kathon CG 5 ppm 5 ppm 5 ppm 5ppm 5 ppm Deionized water and Bal. Bal. Bal. Bal. Bal. other minoringredients ⁽¹⁹⁾Di(hydrogenated tallowyl) dimethyl ammoniumchloride/hydrogenated tallowyl trimethyl ammonium chloride blend ofabout 83:17 weight ratio. ⁽²⁰⁾Di(acyloxyethyl) dimethyl ammoniumchloride wherein the acyl group is derived from soft tallow fatty acidsand with a diester-to-monoester weight ratio of about 11:1.⁽²¹⁾Di(acyloxyethyl) dimethyl ammonium chloride wherein the acyl groupis derived from partially hydrogenated canola fatty acids and with adiester-to-monoester weight ratio of about 11:1.⁽²²⁾Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methyl sulfatewherein the acyl group is derived from partially hydrogenated canolafatty acids. ⁽²³⁾1-Tallow(amidoethyl)-2-tallowimidazoline.

EXAMPLE XVI

XVIa XVIb XVIc XVId XVIe XVIf Ingredients Wt % Wt % Wt % Wt. % Wt % Wt %Arabinogalactan A 5 — — 5 9 15 Arabinogalactan B — 3 — — — —Arabinogalactan C — — 2 — — — Oligosaccharide Mix- — 3 — — — — ture AOligosaccharide Mix- 5 — — — — — ture B Oligosaccharide Mix- — — — — 3 —ture C Oligosaccharide Mix- — — 8 2 — — ture D Fabric softener A⁽¹⁹⁾ 4.5— — — — — Fabric softener B⁽²⁰⁾ — 24 — — — — Fabric softener C⁽²¹⁾ — —26 — — — Fabric softener D⁽²²⁾ — — — 28 28 — Fabric softener E⁽²³⁾ 3.4 —— — — — 1,2-Hexanediol — — 18 — — — 2-Ethyl-1,3-hexanediol — — — 6 — —Neodol 91-8 — — — 5 3 — Pluronic L-35 — — — 1 — — Hexylene glycol — — —— 3 — Hexylene glycol (from — — — 2.5 2.5 — softener active) Ethanol(from softener — 4.2 4.6 2.3 2.3 — active) Perfume B 0.3 1.3 1.3 2 1.21.2 Tenox 6 antioxidant 0.02 0.04 0.04 0.04 0.04 CaCl₂ 0.05 0.4 0.5 — 2— MgCl₂ — — — 1.6 — — HCl to pH 6 to pH to pH to pH 3 to pH 3 — 3.5 3.5Polysorbate 60 — — — — — 1 Deionized water and Bal. Bal. Bal. Bal. Bal.Bal. other minor ingred- ients

EXAMPLE XVII

XVIIa XVIIb XVIIc XVIId XVIIe XVIIf Ingredients Wt % Wt % Wt % Wt. % Wt% Wt % Arabinogalac- 6 — — 15 — 30 tan A Arabinogalac- — 20 — — 10 — tanB Arabinogalac- — — 16 — — — tan C Fabric softener 4.5 — — — — — A⁽¹⁹⁾Fabric softener — 22 25 25 — — B⁽²⁰⁾ Fabric softener 3.4 — — — — — E⁽²³⁾PVPK-15⁽²⁴⁾ 1 3 — — 5 — PVNO⁽²⁵⁾ — — 1 — — — Cellulase(26) — — — 1 — 2—Perfume B 0.4 1.3 1.3 1.3 2 — Perfume C — — — — — 1.5 Polysorbate 60 — —— — 5 1 HCl to pH 5 to pH to pH to pH — — 3.5 3.5 3.5 Kathon CG 5 ppm 5ppm 5 ppm 5 ppm 5 ppm 10 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.water and mi- nor ingredients ⁽¹⁹⁾Di(hydrogenated tallowyl) dimethylammonium chloride/hydrogenated tallowyl trimethyl ammonium chlorideblend of about 83:17 weight ratio. ⁽²⁰⁾Di(acyloxyethyl) dimethylammonium chloride wherein the acyl group is derived from soft tallowfatty acids and with a diester-to-monoester weight ratio of about 11:1.⁽²³⁾1-Tallow(amidoethyl)-2-tallowimidazoline. ⁽²⁴⁾Polyvinylpyrrolidonewith an average molecular weight of about 10,000.⁽²⁵⁾Poly(4-vinylpyridine-N-oxide) with an average molecular weight ofabout 25,000. ⁽²⁶⁾The cellulase consists essentially of a homogeneousendoglucanase component, which is immunoreactive with an antibody raisedagainst a hightly purified 43 kD cellulase derived from Humicolainsolens, DMS 1800, or which is homologous to said 43 kD endoglucanase;the cellulase solution used provides about 5,000 CEVU's per gram.

EXAMPLE XVIII

XVIIIa XVIIIb XVIIIc XVIIId XVIIIe XVIIIf Ingredients Wt % Wt % Wt % Wt.% Wt % Wt % Arabinogalac- 4 5 — 15 — 16 tan A Arabinogalac- — — 5— — — —tan B Arabinogalac- — — — — 6 — tan C Oligosacchar- 6 — — 10 — — ideMixture A Oligosacchar- — 10 — — 6 — ide Mixture B Oligosacchar- 5 ideMixture C Oligosacchar- — — — 5 — 4 ide Mixture D Fabric soft- 4.5 — — —— — ener A Fabric soft- — 22 25 25 — — ener B Fabric soft- 3.4 — — — — —ener E PVPK-15 1 3 — — 5 — PVNO — — 1 — — — Cellulase⁽²⁶⁾ — — — 1 — 2Perfume B 0.4 1.3 1.3 1.3 2 — Perfume C — — — — — 1.5 Polysorbate 60 — —— — 5 1 HCl to pH 5 to pH to pH to pH — — 3.5 3.5 3.5 Kathon CG 3 ppm 3ppm 3 ppm 3 ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.water and mi- nor ingredients

EXAMPLE XIX

XIXa XIXb XIXc XIXd XIXe XIXf Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Arabinogalac- 10 — — — — — tan A Arabinogalac- — 16 — — — — tan BArabinogalac- — — 12 — — — tan C Quaternized — — — 12 — — Arabinogalac-tan A⁽²⁾ Curdlan⁽³⁾ — — — — 8 — Dextran⁽⁴⁾ — — — — — 12 Fabric softener35 35 35 35 35 35 D⁽²²⁾ TMPD⁽²⁷⁾ 5 5 5 5 5 5 Neodol 91-8 6 6.5 6.5 6 6.56.5 Pluronic L-35 1 1 1.5 1 1 1.5 Hexylene gly- 3.1 3.1 3.1 3.1 3.1 3.1col (from soft- ener active) Ethanol (from 2.9 2.9 2.9 2.9 2.9 2.9softener active) TPED⁽²⁸⁾ 0.75 0.75 0.75 0.75 0.75 0.75 DTPA⁽²⁹⁾ 0.010.1 0.01 0.01 0.1 0.01 Perfume 2.5 3 1.8 2.5 3 1.8 MgCl₂ 1.75 1 1 1.75 11 Blue dye 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm HCl to pH to pH to pH topH to pH to pH 6 3.5 3.5 6 3.5 3.5 Kathon CG 3 ppm 3 ppm 3 ppm 3 ppm 3ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal. water and other minoringred- ients ⁽²²⁾Di(acyloxyethyl)(2-hydroxyethyl)methyl ammonium methylsulfate wherein the acyl group is derived from partially hydrogenatedcanola fatty acids. ⁽²⁷⁾2,2,4-Trimethyl-1,3-pentanediol.⁽²⁸⁾Tetrakis-(2-hydroxypropyl) ethylenediamine. ⁽²⁹⁾Sodiumdiethylenetriaminepentaacetate.

EXAMPLE XX

XXa XXb XXc XXd XXe XXf Ingredients Wt % Wt % Wt % Wt % Wt % Wt %Arabino- 6 — — — — — galactan A Arabino- — 10 — — — — galactan BArabino- — — 4 — — — galactan C Quaternized — — — 10 — — Arabino-galactan A⁽²⁾ Curdlan⁽³⁾ — — — — 3 — Dextran⁽⁴⁾ — — — — — 8 Oligo- — — —2 — — saccharide Mixture A Oligo- — — 8 — 5 — saccharide Mixture BOligo- — 6 — — — — saccharide Mixture C Oligo- 6 — — — — 4 saccharideMixture D Fabric 35 35 35 35 35 35 softener D⁽²²⁾ TMPD⁽²⁷⁾ 5 5 5 5 5 5Neodol 91-8 6 6.5 6.5 6 6.5 6.5 Pluronic L-35 1 1 1.5 1 1 1.5 Hexylene3.1 3.1 3.1 3.1 3.1 3.1 glycol (from softener active) Ethanol (from 2.92.9 2.9 2.9 2.9 2.9 softener active) TPED⁽²⁸⁾ 0.75 0.75 0.75 0.75 0.750.75 DTPA⁽²⁹⁾ 0.01 0.1 0.01 0.01 0.1 0.01 Perfume 2.5 3 1.8 2.5 3 1.8MgCl₂ 1.75 1 1 1.75 1 1 Blue dye 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm 6 ppm HClto pH to pH to pH to pH to pH to pH 6 3.5 3.5 6 3.5 3.5 Kathon CG 3 ppm3 ppm 3 ppm 3 ppm 3 ppm 3 ppm Deionized Bal. Bal. Bal. Bal. Bal. Bal.water and other minor ingredientsFollowing are Examples for laundry detergent fabric care compositions inaccordance with the present invention:

EXAMPLE XXI

XXIa XXIb XXIc XXId XXIe Ingredients Wt % Wt. % Wt % Wt. % Wt. %LAS^((a)) 8 8 8 7 7 C25E3^((b)) 3.4 3.4 3.4 3.4 3.4 QAS^((c)) — 0.8 —0.8 0.8 Zeolite A 17 17 17 16 16 Carbonate 13 24 13 22 22 Silicate 1.4 31.4 3 3 Sulfate 25 16 24 12 12 PB4^((d)) 9 8 9 8 7 TAED^((e)) 1.5 1.51.5 1.5 1.5 DETPMP^((f)) 0.25 0.25 0.25 0.25 0.25 HEDP^((g)) 0.3 0.3 0.30.3 0.3 Arabinogalactan A 18 — — 15 14 Arabinogalactan B — 15 — — —Arabinogalactan C — — 20 — — Oligosaccharide Mixture — — — 8 — AOligosaccharide Mixture — — — — 10 D Protease 26 ppm 26 ppm 26 ppm 26ppm 26 ppm MA/AA^((h)) 0.3 0.3 0.3 0.3 0.3 CMC^((i)) 0.2 0.2 0.2 0.2 0.2Photoactivated Bleach — 10 ppm — 10 ppm 10 ppm Brightener 0.09 0.09 0.090.09 0.09 Perfume 0.3 0.3 0.3 0.3 0.3 Silicone antifoam 0.5 0.5 0.5 0.50.5 Moisture and Balance Balance Balance Balance Balance Miscellaneous^((a))Sodium linear C₁₂ alkyl benzene sulphonate. ^((b))A C₁₂—C₁₅predominately linear primary alcohol condensed with an average of 3moles of ethylene oxide. ^((c))(C₁₂—C₁₄)N⁺(CH₃)₂C₂H₄OH) ^((d))Sodiumperborate.4H20. ^((e))Tetraacetyl ethylene diamine. ^((f))Diethylenetriamine penta(methylene phosphonic acid), marketed by Monsanto underthe Trade name Dequest 2060. ^((g))1,1-Hydroxyethane diphosphonic acid.^((h))Copolymer of 1:4 maleic/acrylic acid, average molecular weightabout 70,000–80,000. ^((i))Sodium carboxymethyl cellulose.

EXAMPLE XXII

Nil bleach-containing laundry detergent fabric care compositions ofparticular use in the washing of colored clothing:

XXIIa XXIIb XXIIc XXIId XXIIe Ingredients Wt % Wt. % Wt % Wt. % Wt. %Blown Powder Zeolite A 13 14 13 13 13 Sodium sulfate — 14 — 13 12 LAS2.8 3 2.8 3 2.8 DETPMP 0.4 0.5 0.4 0.5 0.5 CMC 0.4 0.4 0.4 0.4 0.4 MA/AA3.8 4 3.8 3.5 3.8 Agglomerates LAS 5.5 5 5.5 5 5 TAS^((j)) 3 2 3 2 2Silicate 4 4 4 4 4 Zeolite A 8 13 9 12 12 Carbonate 8 7 9 6 7 Spray OnPerfume 0.3 0.3 0.3 0.3 0.3 C45E7^((k)) 4 4 4 4 4 C25E3 1.8 1.8 1.8 1.81.8 Dry additives Na Citrate 9.5 — 10 — — Na Bicarbonate 6.5 3 6.5 3 3Na Carbonate 7.5 5 7.5 4.5 4.5 PVPVI/PVNO^((l)) 0.5 0.5 0.5 0.5 0.5Arabinogalactan A 15 — — 15 — Arabinogalactan B — 12 — — 9Arabinogalactan C — — 12 — — Oligosaccharide Mixture — — — 5 — COligosaccharide Mixture — — — — 9 D Protease 0.026 0.016 0.026 0.0160.016 Lipase 0.009 0.009 0.009 0.009 0.009 Amylase 0.005 — 0.005 — —Cellulase 0.006 0.006 0.006 0.006 0.006 Silicone antifoam 4 3 4 3.5 3Moisture and Miscellan- Balance Balance Balance Balance Balance eous^((j))Sodium tallow alkyl sulphate. ^((k))A C₁₄—C₁₅ predominantly linearprimary alcohol condensed with an average of 7 moles of ethylene oxide^((j))Copolymer of vinyl-imidazole and vinyl-pyrrolidone/poly(4-vinylpyridine)-N-oxide.

EXAMPLE XXIII

Examples of liquid detergent fabric care compositions according to thepresent invention:

XXIIIa XXIIIb XXIIIc XXIIId XXIIIe Ingredients Wt % Wt. % Wt % Wt % Wt %LAS 9 8 — 22 — C25AS^((m)) 4 2 9 — 12 C25E3S^((n)) 1 — 3 — 3.5 C25E7 612 2.5 — 3.5 TFAA^((o)) — — 4.5 — 7.5 QAS — — — 3 — TPKFA^((p)) 2 12 2 —5.5 Canola fatty acids — — 5 — 4 Citric 2 1 1.5 1 1Dodecenyl/tetradecenyl 10 — — 14 — succinic acid Oleic acid 4 1 — 1 —Ethanol 4 6 2 6 2 1,2 Propanediol 4 2 6 6 10 Mono Ethanol Amine — — 5 —8 Tri Ethanol Amine — 7 — — — NaOH (pH) 8 7.5 7.5 8 8 Ethoxylatedtetraethylene 0.5 0.5 0.2 — 0.3 pentamine DETPMP 1 0.5 1 2 — SoilRelease Polymer 0.3 0.3 0.1 — 0.1 PVNO^((q)) — — — — 0.1 ArabinogalactanA 15 — — — — Arabinogalactan B — 12 — — — Arabinogalactan C — — 15 — —Curdlan — — — 12 — Dextran — — — — 10 Protease 50 ppm 40 ppm 30 ppm 0.0860 ppm Lipase — —  2 ppm — 30 ppm Amylase 20 ppm 50 ppm 40 ppm 20 ppm 50ppm Cellulase — —  1 ppm —  4 ppm Boric acid 0.1 — 2 1 2.5 Na formate —1 — — — Ca chloride — — 0.01 — — Bentonite clay — — — 3.5 — Suspendingclay — — — 0.6 — Water and Miscellaneous Bal. Bal. Bal. Bal. Bal.^((m))Sodium C₁₂—C₁₅ alkyl sulfate. ^((n))C₁₂—C₁₅ sodium alkyl sulfatecondensed with an average of 3 moles of ethylene oxide per mole.^((o))C₁₆—C₁₈ alkyl N-methyl glucose amide. ^((p))C12—C14 topped wholecut fatty acids. ^((q))Poly(4-vinylpyridine-N-oxide) dye transferinhibiting agent.

EXAMPLE XXIV

Examples of liquid detergent fabric care compositions according to thepresent invention:

XXIVa XXIVb XXIVc XXIVd XXIVe Ingredients Wt % Wt. % Wt % Wt % Wt % LAS8 8 — 19 — C25AS 4 2 8 — 11 C25E3S 1 — 3 — 3.5 C25E7 5.5 11 2.5 — 3.5TFAA — — 4.5 — 7.5 QAS — — — 3 — TPKFA 2 11 2 — 5 Canola fatty acids — —4.5 — 4 Citric 2 1 1.5 1 1 Dodecenyl/tetradecenyl 9.5 — — 13 — succinicacid Oleic acid 4 1 — 1 — Ethanol 4 6 2 6 2 1,2 Propanediol 4 2 5.5 6 8Mono Ethanol Amine — — 5 — 7 Tri Ethanol Amine — 6 — — — NaOH (pH) 8 7.57.5 8 8 Ethoxylated tetraethylene 0.5 0.5 0.2 — 0.3 pentamine DETPMP 10.5 1 2 — Soil Release Polymer 0.3 0.3 0.1 — 0.1 PVNO — — — — 0.1Arabinogalactan A 12 15 Arabinogalactan B 12 10 Arabinogalactan C 5Oligosaccharide Mixture 5 — — — — A Oligosaccharide Mixture — 3 — — 5 COligosaccharide Mixture — — 12 5 — D Protease 50 ppm 40 ppm 30 ppm 0.0860 ppm Lipase — —  2 ppm — 30 ppm Amylase 20 ppm 50 ppm 40 ppm 20 ppm 50ppm Cellulase — —  1 ppm —  4 ppm Boric acid 0.1 — 2 1 2.5 Na formate —1 — — — Ca chloride — — 0.01 — — Bentonite clay — — — 2.5 — Suspendingclay SD3 — — — 0.5 — Water and Miscellaneous Bal. Bal. Bal. Bal. Bal.

EXAMPLE XXV

Examples of liquid detergent fabric care compositions for fine fabricsaccording to the present invention:

XXVa XXVb XXVc XXVd Ingredients Wt. % Wt % Wt. % Wt. % Arabinogalactan A12 — 2 9 Arabinogalactan B — 9 — — Oligosaceharide Mixture C — — 7 —Oligosaccharide Mixture D — — — 3 C12–15AE1.8S 10.3 9.7 9.7 10.3 Neodol23-9 — 0.3 0.3 — Neodol 45-7 2.9 — — 2.9 C8–10 Amidopropyl — 0.25 0.25 —dimethylamine CFAA^((r)) — 1 1 — C12 trimethylammonium 3.8 — — 3.8chloride Citric Acid 0.75 1.7 1.7 0.75 C12–16 Fatty Acid — 1.2 1.2 —Ethanol 1.5 1.6 1.6 1.5 1,2-Propanediol 2.6 4 4 2.6 Mono Ethanol Amine0.55 0.45 0.45 0.55 Na Formate 0.07 0.45 0.45 0.07 Na Toluene Sulfonate0.25 0.2 0.2 0.25 Borax 0.1 0.5 0.5 0.1 NaOH — 1.7 1.7 — Ethoxylated0.65 0.55 0.55 0.65 Tetraethylenepentamine Ethoxylated — 1.1 1.1 —polyethyleneimine Protease 0.07 0.03 0.03 0.07 Amylase 0.15 0.06 0.060.15 Mannanase 0.15 — — 0.15 Silwet L77 3.6 0.3 0.3 3.6 PVNO 0.25 — —0.25 Suds Suppressor — 0.05 0.05 — Perfume 0.5 0.35 0.35 0.5 Dye 7 ppm —— 7 ppm Water and Miscellaneous Bal. Bal. Bal. Bal. ^((r))C₁₂—C₁₄ alkylN-methyl glucose amide.

EXAMPLE XXVI

Examples of syndet bar fabric detergent fabric care compositions inaccord with the present invention:

XXVIa XXVIb XXVIc Ingredients Wt % Wt. % Wt. % C26 AS 18 18 18 CFAA 5 55 LAS (C11–13) 10 10 10 Sodium carbonate 22 25 20 Sodium pyrophosphate 66 6 STPP^((s)) 6 6 6 Zeolite A 5 5 5 CMC 0.2 0.2 0.2 Polyacrylate (MW1400) 0.2 0.2 0.2 Coconut monethanolamide 5 5 5 Arabinogalactan A 12 —12 Arabinogalactan B — 10 — Oligosaccharide Mixture D — — 5 Amylase —0.02 0.02 Protease — 0.3 0.3 Perfume 0.2 0.2 0.2 Brightener 0.1 0.1 0.1CaSO4 1 1 1 MgSO4 1 1 1 Perfume 0.2 0.3 0.2 Water 4 4 4 Filler^((t))Balance Balance Balance ^((s))Anhydrous sodium tripolyphosphate.^((t))Can be selected from convenient materials such as CaCO₃, talc,clay (Kaolinite, Smectite), silicates, and the like.Following are Examples for fabric care pre-wash and wash additivecompositions in accordance with the present invention:

EXAMPLE XXVII

XXVIIa XXVIIb XXVIIc XXVIId Ingredients Wt. % Wt. % Wt. % Wt. %Arabinogalactan A 15 — — — Arabinogalactan B — 10 — — Arabinogalactan C— — 7 — Curdlan — — — 8 Dye Fixative Agent^((u)) 2 — — — Dye transferInhibitor^((v)) — — — — Polysorbate 60 0.8 0.8 1 0.8 Perfume 0.5 0.5 0.80.5 Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm Deionized Water Bal. Bal. Bal.Bal. ^((u))Cartafix CB from Clariant ^((v))Polyvinvlpyrrolidone 85K

EXAMPLE XXVIII

XXVIIIa XXVIIIb XXVIIIc XXVIIId Ingredients Wt. % Wt. % Wt. % Wt. %Araibinogalactan A 3 10 10 5 Oligosaccharide Mixture 5 — 5 — AOligosaccharide Mixture — 10 — 10 D Dye Fixative Agent^((u)) 2.5 — — —Dye transfer Inhibitor^((v)) 5 7 — — Polysorbate 60 0.5 1 1 0.5 Perfume0.3 1 0.8 0.5 Kathon CG 5 ppm 5 ppm 5 ppm 5 ppm Deionized Water Bal.Bal. Bal. Bal.

EXAMPLE XXIX

XXIXa XXIXb XXIXc XXIXd Ingredients Wt. % Wt. % Wt. % Wt. %Arabinogalactan A 10 7 — — Arabinogalactan B — — 5 — Arabinogalactan C —— — 5 Oligosaccharide Mixture A — — 4 — Oligosaccharide Mixture B — — —5 Oligosaccharide Mixture C 3 — — — Oligosaccharide Mixture D — 7 — —Dye Fixative Agent^((u)) 2.5 — 2 — Dye transfer Inhibitor^((v)) 5 5 3.53.5 Polysorbate 60 0.8 0.7 0.7 1 Perfume 0.5 0.4 0.5 1 Kathon CG 5 ppm 5ppm 5 ppm Deionized Water Bal. Bal. Bal.The compositions of Examples XXVII–XXIX can be diluted with from about 3times to about 30 times to make pre-wash soaking solutions to providefabric care benefits. The compositions of Examples XXVII–XXIX can alsobe added to wash and/or rinse water to provide fabric care benefits.

1. A fabric care composition comprising: (A) from about 0.001 to about20, by weight of the composition, of a fabric care polysaccharide withglobular structure and having a backbone comprising at least some1,3-β-glycosidic linkages for providing a fabric with at least one ofthe following fabric care benefits: wrinkle removal, wrinkle reduction,wrinkle resistance, fabric wear reduction, fabric wear resistance,fabric pilling reduction, fabric color maintenance, fabric color fadingreduction, fabric color restoration, fabric soiling reduction, fabricsoil release, fabric shape retention, and/or fabric shrinkage reduction;(B) optionally, from about 0.01% to about 20%, by weight of thecomposition, of adjunct fabric care oligosaccharide, selected from thegroup consisting of oligosaccharides, oligosaccharide mixtures,substituted versions of said oligosaccharides and/or mixtures,derivatised versions of said oligosaccharides and/or mixtures, andmixtures thereof; (C) to remove and/or reduce wrinkles, an effectiveamount of adjunct wrinkle control agent, selected from the groupconsisting of fiber lubricant, adjunct fabric shape retention polymer,lithium salts, and mixtures thereof; (D) optionally, to reduce surfacetension, and/or to improve performance and formulatability, an effectiveamount of surfactant; (E) optionally, an effective amount to absorbmalodor, of odor control agent; (F) an effective amount to provideolfactory effects of perfume; (G) optionally, an effective amount, tokill, or reduce the growth of microbes, of antimicrobial active; (H)optionally, an effective amount to provide improved antimicrobial actionof aminocarboxylate chelator; (I) optionally, an effective amount ofantimicrobial preservative, in addition to, or in place of saidantimicrobial active; and (J) optionally, an aqueous carrier, saidcomposition optionally being essentially free of any material that wouldsoil or stain fabric under usage conditions.
 2. The composition of claim1 containing from about 0.01% to about 10%, by weight of said fabriccare composition, of said fabric care polysaccharide.
 3. The compositionof claim 1 wherein said fabric care polysaccharide has a molecularweight of from about 5,000 to about 500,000.
 4. The composition of claim1 wherein said fabric care polysaccharide has a size of from about 2 nmto about 300 nm.
 5. The composition of claim 1 wherein said fabric carepolysaccharide is selected from the group consisting of arabinogalactan,pachyman, curdlan, callose, paramylon, sceleroglucan, lentinan,lichenan, lamirarin, szhizophyllan, grifolan, sclerotinia selerotiorumglucan, ompharia lapidescence glucan, and mixtures thereof.
 6. Thecomposition of claim 5 wherein said fabric care polysaccharide isarabinogalactan.
 7. The composition of claim 6 wherein saidarabinogalactan has a molecular weight of from about 6,000 to about500,000.
 8. The composition of claim 7 wherein said arabinogalactan isselected from the group consisting of: arabinogalactan having amolecular weight of from about 14,000 to about 22,000; arabinogalactanhaving a molecular weight of from about 60,000 to about 120,000; andmixtures thereof.
 9. The composition of claim 1 wherein said fabric carecomposition additionally comprises adjunct fabric care oligosaccharideselected from the group consisting of oligosaccharides, oligosaccharidemixtures, substituted versions of said oligosaccharides and/or mixtures,derivatised versions of said oligosaccharides and/or mixtures, andmixtures thereof.
 10. The composition of claim 9 wherein the weightratio between said adjunct fabric care oligosaccharides and the fabriccare polysaccharides is from about 1:99 to about 99:1.
 11. Thecomposition of claim 9 containing from about 0.001% to about 20%, byweight of said fabric care composition, of said adjunct fabric careoligosaccharide.
 12. The composition of claim 9 wherein said adjunctfabric care oligosaccharide comprises oligosaccharides with a degree ofpolymerization of from about 1 to about 15, and wherein each monomer isselected from the group consisting of sacharide containing 5 or 6 carbonatoms.
 13. The composition of claim 12 wherein said adjunct fabric careoligosaccharide comprises isomaltooligosaccharides with a degree ofpolymerization of from about 2 to about 10, wherein the glucose unitsare linked by α-linkages and/or β-linkages.
 14. The composition of claim13 wherein said isomaltooligosaccharides contain from about 3 to about 7glucose units which are linked by 1,2-α; 1,3-α; 1,4-α-, and1,6-α-linkages, and mixtures of these linkages.
 15. The composition ofclaim 12 wherein said adjunct fabric care oligosaccharide is selectedfrom the group consisting of isomaltose, isomaltotriose,isomaltotetraose, isomaltooligosaccharide, fructooligosaccharide,levooligosaccharides, galactooligosaccharide, xylooligosaccharide,gentiooligosaccharides, disaccharides, glucose, fructose, galactose,xylose, mannose, arabinose, rhamnose, maltose, sucrose, lactose,maltulose, ribose, lyxose, allose, altrose, gulose, idose, talose,trehalose, nigerose, kojibiose, lactulose, oligosaccharides,maltooligosaccharides, trisaccharides, tetrasaccharides,pentasaccharides, hexasaccharides, oligosacharides from partialhydrolysates of natural polysaccharide sources, and mixtures thereof.16. The composition of claim 1 wherein said fabric care compositionadditionally comprises a fiber lubricant.
 17. The composition of claim16 wherein said fiber lubricant is silicone.
 18. The composition ofclaim 17 wherein said silicone is volatile and is present at a level offrom about 0.1% to about 5%, by weight of the composition.
 19. Thecomposition of claim 18 wherein said volatile silicone has the formula[(CH₃)₂SiO)]₅.
 20. The composition of claim 17 wherein said silicone ispresent at a level of from about 0.1% to about 5% by weight of thecomposition, and is selected from the group consisting of: (A) polyalkylsilicone with the following structure:A—Si(R₂)—O—[Si(R₂)—O—]_(q)—Si(R₂)—A wherein each R is an alky, ahydroxy, or a hydroxyalkyl group, and mixtures thereof, having less thanabout 8 carbon atoms; q is an integer from about 7 to about 8,000; eachA is a group selected from hydrogen, methyl, methoxy, ethoxy, hydroxy,and propoxy; (B) silicone having the formula:HO—Si(CH₃)₂—O]_(x)—{Si(OH)[(CH₂)₃—NH—(CH₂)₂—NH₂]O}_(y)—H wherein x and yare integers; (C) silicone material having the formula:(R¹)_(a)G_(3-a)—Si—(—OSiG₂)_(n)—OSiG_(b)(R¹)_(2-b))_(m)—O—SiG_(3-a)(R¹)_(a) wherein G is selected from the group consistingof hydrogen OH, and/or C₁–C₅ alkyl; a denotes 0 or an integer from 1 to3; b denotes 0 or 1; the sum of n+m is a number from 1 to about 2,000,R¹ is a monovalent radical of formula C_(p)H_(2p)L in which p is aninteger from 2 to 4 and L is selected from the group consisting of:—N(R²)CH₂—CH₂—N(R²)₂; —N(R²)₂; —N⁺(R²)₃ A⁻; and —N⁺(R²)C₂—CH₂N⁺H₂ A⁻wherein each R² is chosen from the group consisting of hydrogen, a C₁–C₅saturated hydrocarbon radical, and each A⁻ denotes compatible anion; (D)silicones having the formula:R³—N⁺(CH₃)₂—Z—[Si(CH₃)₂O]_(f)—Si(CH₃)₂—Z—N⁺(CH₃)₂—R³.2CH₃COO⁻ whereinZ=—CH₂—CH(OH)—CH₂O—CH₂)₃— R³ denotes a long chain alkyl group; and fdenotes an integer of at least about 2; and (E) mixtures thereof. 21.The composition of claim 20 wherein said silicone is polydialkylsiliconeA—Si(R₂)—O—[Si(R₂)—O—]_(q)—Si(R₂)—A with A and R groups being methyl.22. The composition of claim 1 wherein said fabric care compositionadditionally comprises from about 0.05% to about 10% by weight of thecomposition, of shape retention polymer which is a homopolymer and/or acopolymer.
 23. The composition of claim 22 wherein said shape retentionpolymer is a homopolymer and/or copolymer having a glass transitiontemperature of from about −20° C. to about 150° C. and comprisingmonomers selected from the group consisting of low molecular weightC₁–C₆ unsaturated organic mono-carboxylic and/or polycarboxylic acids;esters of said acids with C₁–C₁₂ alcohols; amides and imides of saidacids; low molecular weight unsaturated alcohols; esters of lowmolecular weight unsaturated alcohols with low molecular weightcarboxylic acids; ethers of low molecular weight unsaturated alcohols;polar vinyl heterocyclics; unsaturated amines and amides; salts of saidamines with low molecular weight carboxylic acids; C₁–C₄ alkylquaternized derivatives of said amines; vinyl sulfonate; low molecularweight unsaturated hydrocarbons and derivatives; and mixtures thereof.24. The composition of claim 23 wherein said shape retention polymermonomers are selected from the group consisting of: acrylic acid,methacrylic acid, crotonic acid, maleic acid and its half esters,itaconic acid, and esters of said acids with methanol, ethanol,1-propanol, 2-propanol, 1-butanol, 2-methyl-1-propanol, 1-pentanol,2-pentanol, 3-pentanol, 2-methyl-1-butanol, 1-methyl-1-butanol,3-methyl-1-butanol, 1-methyl-1-pentanol, 2-methyl-1-pentanol,3-methyl-1-pentanol, t-butanol, cyclohexanol, 2-ethyl-1-butanol,neodecanol, 3-heptanol, benzyl alcohol, 2-octanol, 6-methyl-1-heptanol,2-ethyl-1-hexanol, 3,5-dimethyl-1-hexanol, 3,5,5-trimethyl-1-hexanol,1-decanol, 1-dodecanol, and mixtures thereof; methyl acrylate; ethylacrylate; t-butyl acrylate; methyl methacrylate; hydroxyethylmethacrylate; methoxy ethyl methacrylate; N,N-dimethylacrylamide;N-t-butyl acrylamide; maleimides; vinyl alcohol; allyl alcohol; vinylacetate; vinyl propionate; methyl vinyl ether; vinyl pyrrolidone; vinylcaprolactam; vinyl pyridine; vinyl imidazole; vinyl amine; diethylenetriamine; dimethylaminoethyl methacrylate; ethenyl formamide; vinylsulfonate; ethylene; propylene; butadiene; cyclohexadiene; vinylchloride; vinylidene chloride; salts thereof and alkyl quaternizedderivatives thereof; and mixtures thereof.
 25. The composition of claim24 wherein said shape retention polymer monomers are selected from thegroup consisting of: acrylic acid; methacrylic acid; methyl acrylate;ethyl acrylate; methyl methacrylate; t-butyl acrylate; t-butylmethacrylate; n-butyl acrylate; n-butyl methacrylate; isobutylmethacrylate; 2-ethylhexyl methacrylate; vinyl alcohol;dimethylaminoethyl methacrylate; N,N-dimethyl acrylamide; N,N-dimethylmethacrylamide; N-t-butyl acrylamide; vinylpyrrolidone; vinyl pyridine;adipic acid; diethylenetriamine; salts thereof and alkyl quaternizedderivatives thereof; and mixtures thereof.
 26. The composition of claim22 wherein said shape retention polymer is a copolymer which containsboth hydrophilic monomer and hydrophobic monomer.
 27. The composition ofclaim 26 wherein said shape retention copolymer has a hydrophobicmonomer/hydrophilic monomer ratio of from about 95:5 to about 20:80, byweight of the copolymer.
 28. The composition of claim 22 wherein saidshape retention polymer comprises silicone-containing graft and blockcopolymers having the following properties: (1) the silicone portion iscovalently attached to the non-silicone portion; (2) the molecularweight of the silicone portion is from about 1,000 to about 50,000; andthe non-silicone portion must render the entire copolymer soluble ordispersible in the fabric care composition vehicle and permit thecopolymer to deposit on/adhere to the treated fabrics.
 29. Thecomposition of claim 28 wherein said shape retention polymer has anaverage molecular weight of from about 10,000 to about 1,000,000 andcomprises from about 5% to about 50% of silicone containing monomers.30. The composition of claim 1 wherein said fabric care compositionadditionally comprises from about 0.1% to about 10% by weight of theusage composition, of lithium salt, or hydrate thereof, selected fromthe group consisting of: lithium bromide, lithium lactate, lithiumchloride, lithium tartrate, lithium bitartrate, and mixtures thereof.31. The composition of claim 1 wherein said fabric care compositionadditionally comprises of from about 0.01% to about 5%, by weight of theusage composition, of an odor control agent selected from the groupconsisting of cyclodextrin, zinc salt, copper salt, water solublecarbonate salt, water soluble bicarbonate salt, water soluble anionicpolymer, and mixtures thereof.
 32. The composition of claim 1additionally containing at least one of the following adjunct materials:fiber lubricant, shape retention polymer, lithium salt, odor controlagent, surfactant, antimicrobial active and/or antibacterialpreservative, chelating agent, enzyme, antioxidant, static controlagent, fabric softening active, suds suppressor, dye transfer inhibitingagent, dye fixing agent, soil release agent, brightener, dispersant,insect repelling agent, moth repelling agent, and/or liquid carrier. 33.A fabric care composition according to claim 1 which is a rinse-addedcomposition containing from about 0.1% to about 50%, by weight of thecomposition, of said fabric care polysaccharide, and optionallycontaining fabric softener active at a level of from about 1% to about75%, by weight of the composition.
 34. The composition of claim 22wherein said fabric softening active has an Iodine Value of at leastabout 40, and has a phase transition temperature of less than about 50°C., said composition additionally comprising: (A) optionally, less thanabout 40%, by weight of the composition, of principal solvent having aClogP of from about −2.0 to about 2.6; (B) optionally, from about 0.1%to about 10%, by weight of the composition, of electrolyte; (C)optionally, from 0.1% to about 15%, by weight of the composition ofphase stabilizer, preferably being a surfactant containing alkoxylationand having an HLB of from about 8 to about 20; and (D) the balancewater, minor ingredients and/or water soluble solvents.
 35. The fabriccare composition of claim 33 additionally containing at least aneffective amount of at least one of the following adjunct materials:adjunct fabric care oligosaccharide, perfume, dye transfer inhibitingage, dye fixative agent, chlorine scavenging agent, soil release agent,chemical stabilizer, silicone, antimicrobial active and/or preservative,metal chelating agent, colorant, enzyme, brightener, liquid carrier, ormixtures thereof.
 36. A fabric care composition according to claim 1which is a laundry detergent composition containing from about 0.2% toabout 30% by weight of the composition, of said fabric carepolysaccharide and from about 0.1% to about 60% by weight of thecomposition, of surfactant, and additionally containing at least one ofthe following adjunct materials: adjunct fabric care oligosaccharide,perfume, builder, bleaching agent, dye transfer inhibiting agent, dyefixing agent, odor control agent, brightener, dispersant, heavy metalchelating agent, enzyme, suds suppressor, fabric softening agent, soilrelease agent, and/or liquid carrier.
 37. The composition if claim 36wherein said composition is in a form selected from the group consistingof liquid, powder, granules, tablets, paste, gel, foam, spray, bar, andstick, wherein said composition is optionally contained in a pouch orattached to a releasable substrate.
 38. A fabric care compositionaccording to claim 1 which is an aqueous composition to apply to fabricin the dying step, containing said fabric care polysaccharide at a levelof from about 0.01% to about 25%, by weight of the compositions, andoptionally containing fabric softener active at a level of from about0.05% to about 10%, by weight of the composition.
 39. A fabric carecomposition according to claim 1 which is a dryer-added fabric softeningcomposition containing said fabric care polysaccharide at a level offrom about 0.01% to about 40%, by weight of the composition, and fabricsoftener active at a level of from about 1% to about 99%, by weight ofthe composition.
 40. The fabric care composition of claim 38additionally containing at least an effective amount of at least one ofthe following adjunct materials: adjunct fabric care oligosaccharide,chlorine scavenging agent, dye transfer inhibiting agent, dye fixativeagent, chemical stabilizer, silicone, antimicrobial active and/orpreservative, metal chelating agent, brightener, enzyme, soil releaseagent, liquid carrier, or mixtures thereof.
 41. An article ofmanufacture comprising a fabric care composition comprising from about0.001% to about 20% of a fabric care polysaccharide with globularstructure and having a backbone comprising at least some 1,3β-glycosidic linkages for providing a fabric with at least one of thefollowing fabric care benefits: wrinkle removal, wrinkle reduction,wrinkle resistance, fabric wear reduction, fabric wear resistance,fabric pilling reduction, fabric color maintenance, fabric color fadingreduction, fabric color restoration, fabric soiling reduction, fabricsoil release, fabric shape retention, and/or fabric shrinkage reduction,and an effective amount of adjunct wrinkle control agent selected fromthe group consisting of fiber lubricant, adjunct fabric shape retentionpolymer, lithium salts, and mixtures thereof, association withinstructions for use which direct the consumer to apply at least aneffective amount of said polysaccharide to provide at least one of saidfabric care benefits.
 42. The article of manufacture of claim 41,wherein said composition is an aqueous composition containing from about0.1% to about 5%, by weight of said fabric care composition, of saidfabric care polysaccharide.
 43. The article of manufacture of claim 41wherein said spray dispenser comprises a trigger spray device.
 44. Thearticle of manufacture of claim 41 wherein said spray dispensercomprises a non-manually operated spray dispenser.
 45. The article ofmanufacture of claim 44 wherein said non-manually operated spraydispenser is selected from the group consisting of: powered sprayer; airaspirated sprayer; liquid aspirated sprayer; electrostatic sprayer; andnebulizer sprayer.
 46. The article of manufacture of claim 41 whereinsaid composition additionally contains at least one of the followingadjunct materials: adjunct fabric care oligosaccharide, fiber lubricant,shape retention polymer, lithium salt, odor control agent, surfactant,antimicrobial active and/or antibacterial preservative, metal chelatingagent, enzyme, antioxidant, static control agent, fabric softeningactive, dye transfer inhibiting agent, dye fixative agent, soil releaseagent, suds suppressor, brightener, insect repelling agent, mothrepelling agent, and/or liquid carrier.
 47. The article of manufactureof claim 41 in association with instructions for use to direct theconsumer to apply at least an effective amount of said compositionand/or said fabric care polysaccharide to said fabric, to provide saidfabric with at least one of the following fabric care benefits: wrinkleremoval, wrinkle reduction, wrinkle resistance, fabric wear reduction,fabric wear resistance, fabric pilling reduction, fabric colormaintenance, fabric color fading reduction, fabric color restoration,fabric soiling reduction, fabric soil release, fabric shape retention,and/or fabric shrinkage reduction.
 48. The article of manufacture ofclaim 47 wherein said instructions for use direct the consumer to applyan amount of composition to provide from about 0.005% to about 4%, byweight of the fabric.
 49. The article of manufacture of claim 47 whereinsaid instructions for use direct the consumer to apply the compositionto the fabric in combination with stretching and/or smoothing of fabric,to provide effective wrinkle removal.
 50. An article of manufacturecomprising the composition of claim 1 to be applied directly to saidfabric in a manner such that excessive amounts of the fibric carecomposition are prevented from being released to the open environment,packaged in association with instructions for use which direct theconsumer to apply at least an effective amount of said fabric carepolysaccharide with globular structure to said fabric in said manner toprovide said fabric care benefits.
 51. The article of claim 50 whereinsaid composition contains from about 0.01% to about 2% of fabric carepolysaccharide with globular structure, by weight of the composition.52. An article of manufacture comprising the composition of claim 1 topretreat said fabric before washing, packaged in association withinstructions for use which direct the consumer to apply at least aneffective amount of said composition to said fabric to provide saidfabric care benefits.
 53. An article of manufacture comprising thecomposition of claim 1 which is a wash additive composition, packaged inassociation with instructions for use which direct the consumer to applyat least an effective amount of said composition to said fabric toprovide said fabric care benefits.
 54. An article of manufacturecomprising the composition of claim 1 which is a laundry detergentcomposition, packaged in association with instructions for use whichdirect the consumer to apply at least an effective amount of saidcomposition to said fabric to provide the fabric care benefits.
 55. Anarticle of manufacture comprising the composition of claim 1 which is arinse additive composition, packaged in association with instructionsfor use which direct the consumer to apply at least an effective amountof said composition to said fabric to provide said fabric care benefits.56. An article of manufacture comprising the composition of claim 1 toapply to fabric in the drying step, packaged in association withinstructions for use which direct the consumer to apply at least aneffective amount of said composition to sad fabric to provide saidfabric care benefits.
 57. The article of claim 41 wherein saidinstructions for use include pictures and/or icons.
 58. Fabric havingimproved characteristics having an effective amount of a fabric carepolysaccharide with globular structure and having a backbone comprisingat least some 1,3 β-glycosidic linkages attached thereto, an effectiveamount of adjunct wrinkle control agent selected from the groupconsisting of fiber lubricant, adjunct fabric shape retention polymer,lithium salts, and mixtures thereof, and having an effective amount toprovide olfactory effects of perfume.
 59. The fabric of claim 58 whereinsaid fabric comprises from about 0.005% to about 4%, by weight of thefabric of said fabric care polysaccharide.
 60. The fabric of claim 58wherein said fabric is made of fibers selected from the group consistingof natural fibers, synthetic fibers, and mixtures thereof.
 61. Thefabric of claim 60 wherein said fabric is made of fibers selected fromthe group consisting of: cellulosic fibers, proteinaceous fibers,synthetic fibers, long vegetable fibers, and mixtures thereof.
 62. Thefabric of claim 61 wherein said fabric is selected from the groupconsisting of cotton, rayon, linen, Tencel, silk, wool and relatedmammalian fibers, polyester, acrylic, nylon, jute, flax, ramie, coir,kapok, sisal, henequen, abaca, hemp, sunn, and mixtures thereof.
 63. Thefabric of claim 62 wherein said fabric is selected from the groupconsisting of cotton, rayon, linen, polyester/cotton blends, silk, wool,polyester, acrylic, nylon, and mixtures thereof.
 64. A method forproviding a fabric with a fabric care benefit selected from the groupconsisting of: wrinkle removal, wrinkle reduction, wrinkle resistance,fabric wear reduction, fabric wear resistance, fabric pilling reduction,fabric color maintenance, fabric color fading reduction, fabric colorrestoration, fabric soiling reduction, fabric soil release, fabric shaperetention, fabric shrinkage reduction, and mixtures thereof, whereinsaid method comprises contacting said fabric with an effective amount ofa fabric care composition comprising from about 0.001% to about 20 of afabric care polysaccharide with globular structure and having a backbonecomprising an effective amount of adjunct wrinkle control agent selectedfrom the group consisting of fiber lubricant, adjunct fabric shaperetention polymer, lithium salts, and mixtures thereof oligosaccharide,fiber lubricant, shape retention polymer, lithium salt, odor controlagent, an antimicrobial active and/or antibacterial preservativesurfactant, chelating agent, enzyme, antioxidant, static control agent,fabric softening active, dye transfer inhibiting agent, dye fixingagent, soil release agent, brightener, suds suppressor, builder,bleaching agent, dispersant, insect repelling agent, moth repellingagent, and/or liquid carrier.
 65. The method of claim 64 wherein saidfabric care composition is an aqueous composition containing from about0.1% to about 5%, by weight of said fabric care composition, of saidfabric care polysaccharide.
 66. The method according to claim 64 whereinsaid aqueous composition is sprayed onto said fabric as droplets byusing a spray dispenser.
 67. The method of claim 66 wherein said aqueouscomposition is sprayed onto said fabric as droplets by using a spraydispenser, in combination with stretching and/or smoothing of saidfabric.
 68. The method of claim 66 wherein said spray dispensercomprises a trigger spray device.
 69. The method of claim 66 whereinsaid spray dispenser comprises a non-manually operated sprayer selectedfrom the group consisting of: power sprayer; air aspirated sprayer;liquid aspirated sprayer; electrostatic sprayer; and nebulizer sprayer.70. The method of claim 66 wherein said droplets have a weight averagediameter of from about 5 μm to about 250 μm.
 71. The method according toclaim 65 wherein said fabric is dipped and/or soaked in said fabric carecomposition, followed by a squeezing step and/or a drying step.
 72. Themethod according to claim 64 wherein said fabric care compositioncomprises an aqueous composition containing from about 0.5% to about40%, by weight of said fabric care composition, of said fabric carepolysaccharide, and wherein said fabric is dipped and/or soaked in saidfabric care composition, followed by a laundering step.
 73. The methodaccording to claim 65 wherein said fabric care composition contains fromabout 0.2% to about 30% by weight of the composition, of said fabriccare polysaccharide and from about 0.1% to about 60% by weight of thecomposition, of surfactant, and additionally contains at least one ofthe following adjunct materials: adjunct fabric care oligosaccharide,perfume, builder, bleaching agent, dye transfer inhibiting agent, dyefixing agent, odor control agent, brightener, dispersant, heavy metalchelating agent, enzyme, suds suppressor, fabric softening aactive, soilrelease agent, and/or liquid carrier.
 74. The method according to claim64 wherein said fabric care composition is a rinse-added compositioncontaining from about 0.1% to about 50%1, by weight of the composition,of said fabric care polysaccharide, and optionally containing fabricsoftener active at a level of from about 1% to about 75%, by weight ofthe composition.
 75. The method of claim 74 wherein said fabric carecomposition additionally coins at least one of the following adjunctmaterials: adjunct fabric care oligosaccharide, perfume, odor controlagent, dye transfer inhibiting agent, dye fixative agent, chlorinescavenging agent, soil release agent, chemical stabilizer, silicone,antimicrobial active and/or preservative, material chelating agent,colorant, enzyme, brightener, bluing agent, liquid carrier, or mixturesthereof.
 76. The method according to claim 64 wherein said fabric carecomposition is an aqueous composition to apply to fabric in the dryingstep, containing said fabric care polysaccharide at a level of fromabout 0.01% to about 25%, by weight of the composition, and optionallycontaining fabric softener active at a level of from about 0.05% toabout 10%, by weight of the composition.
 77. The method according toclaim 76 wherein said composition is applied from a spray device. 78.The method according to claim 64 wherein said fabric care composition isa dryer-added fabric softening composition containing said fabric carepolysaccharide at a level of from about 0.01% to about 40%, by weight ofthe composition, and fabric softener active at a level of from about 1%to about 99%, by weight of the composition.
 79. The method according toclaim 78 wherein said composition is released from a flexible substrate.80. The method of claim 76 wherein said composition additionallycontains at least one of the following adjunct materials: adjunct fabriccare oligosaccharide, static control agent, distributing agent, perfume,fiber lubricant, adjunct shape retention polymer, lithium salt, odorcontrol agent, dye transfer inhibiting agent, dye fixative agent,chlorine scavenging agent, soil release agent, brightener, heavy metalchelating agent, enzyme, antimicrobial active, antibacterialpreservative, aminocarboxylate chelating agent, antioxidant, and/orliquid carrier.
 81. A method for removing fabric wrinkles by treatingsaid fabric with an effective amount of the composition of claim
 1. 82.A method for reducing fabric shrinkage by treating said fabric with aneffective amount of the composition of claim
 1. 83. A method forreducing fabric wear by treating said fabric with an effective amount ofthe composition of claim
 1. 84. A method for reducing the scratchy feelof wool fabric articles by treating said article with an effectiveamount of the composition of claim
 1. 85. A method for providing fabriccolor care benefits selected from the group consisting of fabric colormaintenance, fabric color fading reduction, fabric color restoration,and mixtures thereof, said method comprising treating said fabric withan effective amount of the composition of claim
 1. 86. An article ofmanufacture comprising the composition of claim 1 to be applied directlyto a garment in a manner such that excessive amounts of the fabric carecomposition are prevented from being released to the open environment,packaged in association with instructions for use which direct theconsumer to apply at least an effective amount of said fabric carepolysaccharide with globular structure to said garment in said manner toprovide said fabric care benefits.
 87. The article of claim 86 whereinsaid composition contains from about 0.01% to about 2% of fabric carepolysaccharide with globular structure, by weight of the composition.